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WO2021212703A1 - Chlorinated fatty acid ester environment-friendly plasticizer and preparation method therefor - Google Patents

Chlorinated fatty acid ester environment-friendly plasticizer and preparation method therefor Download PDF

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Publication number
WO2021212703A1
WO2021212703A1 PCT/CN2020/109034 CN2020109034W WO2021212703A1 WO 2021212703 A1 WO2021212703 A1 WO 2021212703A1 CN 2020109034 W CN2020109034 W CN 2020109034W WO 2021212703 A1 WO2021212703 A1 WO 2021212703A1
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WIPO (PCT)
Prior art keywords
fatty acid
chlorinated
preparation
acid methyl
palm oil
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PCT/CN2020/109034
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French (fr)
Chinese (zh)
Inventor
邵广伟
田秀娟
贾辉
于英杰
谭德敏
Original Assignee
山东岩海建设资源有限公司
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Publication of WO2021212703A1 publication Critical patent/WO2021212703A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the invention relates to the technical field of plasticizers, in particular to a chlorinated fatty acid ester environmentally friendly plasticizer and a preparation method thereof.
  • Plasticizers are the most important chemical additives in the processing of plastics, rubber and other products. There are many types of plasticizers, among which phthalates (butyl ester and octyl ester) are the most commonly used. With the enhancement of human environmental protection awareness, the toxicity of plasticizers has attracted more and more attention. Traditional phthalate plasticizers have been banned in many fields abroad due to the suspected carcinogenicity.
  • Chlorinated fatty acid ester is an environmentally friendly plasticizer developed with oil as raw material, but current chlorinated fatty acid ester products generally use waste oil and acidified oil such as waste oil and swill oil as raw materials, and the preparation process is difficult to control. The quality is unstable.
  • the purpose of the present invention is to provide an environmentally friendly plasticizer for chlorinated fatty acid esters and a preparation method thereof.
  • the preparation method provided by the invention uses palm oil as a raw material to prepare a chlorinated fatty acid ester environmentally friendly plasticizer, the entire preparation process is easy to control, and the product quality is stable and non-toxic.
  • a preparation method of chlorinated fatty acid ester environmental protection plasticizer including the following steps:
  • the temperature of the transesterification reaction is 65-75°C, and the time is 0.5-1.5h;
  • the acid value of the palm oil is ⁇ 0.6mgKOH/g, the moisture content is ⁇ 0.15wt%, and the iodine value is 15-38; the mass percentage of sodium methoxide in the sodium methoxide methanol solution is 27.0-31.0%;
  • the mass percentage of palm oil is 85.0-86.4%
  • the mass percentage of methanol is 12.9-14.2%
  • the sodium methoxide methanol solution is The mass percentage content is 0.6 to 0.9%.
  • the vacuum degree of the rectification is -0.09 ⁇ -0.095Mpa
  • the reflux ratio is 0 ⁇ 2
  • the bottom temperature is 220 ⁇ 240°C
  • the top temperature is 170 ⁇ 200°C
  • the number of plates is 25 ⁇ 30. .
  • the temperature of the chlorination reaction is 85-115°C.
  • the step (3) before the chlorination reaction, it further includes mixing refined fatty acid methyl esters and palm oil; the mass ratio of the refined fatty acid methyl esters to palm oil is (1-9):1.
  • the density of the chlorinated material at the end of the chlorination reaction is 1.06-1.25 g/cm 3 .
  • the density of the chlorinated material at the end of the chlorination reaction is 1.06 to 1.18 g/cm 3 .
  • the chlorinated material before mixing the chlorinated material with the stabilizer, it further includes: degassing the chlorinated material, the temperature of the degassing is 60-90°C, and the degassing until the acid value of the chlorinated material is ⁇ 0.5mgKOH /g.
  • the stabilizer is composed of ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxidized soybean oil, and an anti-ultraviolet agent, and the ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil
  • the mass ratio with the anti-ultraviolet agent is 1:(0 ⁇ 20):(0 ⁇ 20):(0.05 ⁇ 0.1);
  • the added amount of the stabilizer is 0.3-3% of the mass of the chlorinated material.
  • the invention also provides an environmentally friendly chlorinated fatty acid ester plasticizer prepared by the preparation method described in the above scheme.
  • the present invention provides a method for preparing a chlorinated fatty acid ester environmentally friendly plasticizer.
  • the present invention uses palm oil to prepare fatty acid methyl esters, and mixes the refined fatty acid methyl esters with a stabilizer after chlorination to obtain the chlorinated fatty acid of the present invention
  • Ester environmentally friendly plasticizer is a natural fat, rich in resources, stable in ingredients, and low in cost.
  • the prepared plasticizer product is stable in quality and non-toxic.
  • the entire preparation process of the present invention is easier to control; further, the present invention You can choose to directly chlorinate the refined fatty acid methyl ester or mix it with palm oil before chlorination, and control the end point of the chlorination reaction according to the density requirement, so as to obtain a series of environmentally friendly chlorinated fatty acid ester plasticizers with different densities.
  • the preparation method provided by the invention is easy to control the entire reaction process, the production process is environmentally friendly and economical, and the operation is simple, which is suitable for large-scale industrial production.
  • the invention also provides an environmentally friendly chlorinated fatty acid ester plasticizer prepared by the preparation method described in the above scheme.
  • the chlorinated fatty acid ester environmental protection plasticizer product provided by the invention has stable quality, does not contain heavy metals and o-benzene substances, has good compatibility with PVC, has excellent flame retardant and environmental protection performance, and is low in price. It can be widely used Films, artificial leather, plastic floors, wire and cable sheaths and other PVC fields can also replace chlorinated paraffin in the polyurethane field.
  • the invention provides a preparation method of a chlorinated fatty acid ester environmentally friendly plasticizer, which comprises the following steps:
  • the acid value of the palm oil is preferably ⁇ 0.6 mgKOH/g, more preferably 0.1 to 0.5 mgKOH/g, the moisture content is preferably ⁇ 0.15 wt%, more preferably 0.05 to 0.1 wt%, and the iodine value is preferably 15-38, more preferably 20-35; the purity of the methanol is preferably ⁇ 99.0%; the mass percentage of sodium methoxide in the sodium methoxide methanol solution is preferably 27.0-31.0%, more preferably 28.0-30.0%.
  • a commercially available methanol solution of sodium methoxide can be used directly for dosing.
  • the mass percentage of the palm oil is preferably 85.0-86.4%, more preferably 85.5-16%.
  • the mass percentage of the methanol is preferably 12.9 to 14.2%, more preferably 13 to 14%.
  • the mass percentage of methanol in the present invention does not include the methanol introduced in the sodium methoxide methanol solution, and the mass of the sodium methoxide methanol solution
  • the percentage content is preferably 0.6 to 0.9%, more preferably 0.7 to 0.8%.
  • the temperature of the transesterification reaction is preferably 65-75°C, more preferably 68-72°C, and the time of the transesterification reaction is preferably 0.5-1.5 h, more preferably 1 h.
  • the transesterification reaction is preferably carried out in a transesterification reactor.
  • palm oil is preferably preheated to 60° C. and then put into the transesterification reactor, and then methanol and sodium methoxide methanol solution are sequentially added.
  • palm oil and methanol undergo transesterification under the catalysis of sodium methoxide to generate fatty acid methyl esters and glycerin.
  • the product of the transesterification reaction is a mixture of fatty acid methyl esters and glycerol; in the present invention, crude fatty acid methyl esters are preferably separated from the transesterification reaction product through post-treatment; the post-treatment preferably includes the following steps: After the obtained transesterification reaction product is allowed to stand for stratification, the crude glycerin in the lower layer is discharged, and the remaining materials are subjected to vacuum distillation to obtain crude fatty acid methyl esters.
  • the vacuum degree of the vacuum distillation is preferably -0.06 to -0.09 MPa, and the temperature of the vacuum distillation is preferably 60 to 90°C; the present invention recovers methanol through vacuum distillation and recycles the methanol. .
  • the present invention rectifies the crude fatty acid methyl esters to obtain refined fatty acid methyl esters.
  • the rectification is preferably carried out in a rectification tower.
  • the vacuum degree of the rectification is preferably -0.09 ⁇ -0.095Mpa, and the reflux ratio is preferably 0-2, more preferably 1-2.
  • the number is preferably 25 to 30, the bottom temperature is preferably 220 to 240°C, more preferably 225 to 235°C, and the top temperature is preferably 170 to 200°C, more preferably 180 to 190°C; the present invention divides the flow through the rectification tower
  • the refined fatty acid methyl ester is obtained from the top of the tower, and the bottom of the tower is the still residue with incomplete reaction; the yield of the refined fatty acid methyl ester of the present invention is greater than or equal to 96.5%.
  • refined fatty acid methyl esters can be obtained through rectification, and the incompletely reacted materials can be prevented from participating in the subsequent chlorination reaction. There are methyl esters, monoglycerides, diglycerides, etc. in the incompletely reacted materials, and the hydroxyl groups in them will seriously affect The application performance of the product.
  • the refined fatty acid methyl ester is subjected to a chlorination reaction under the condition of chlorine gas to obtain a chlorinated material.
  • the temperature of the chlorination reaction is preferably 85-115°C, more preferably 90-110°C; the chlorination reaction is preferably carried out in a chlorination reaction tower; in the present invention, the refined fatty acid methyl ester is preferably beaten Enter the chlorination reaction tower, turn on the circulating pump, pass in chlorine gas, control the circulating water flow of the condenser, and maintain the reaction temperature at 85-115°C.
  • the chlorination reaction preferably further includes mixing refined fatty acid methyl esters and palm oil, that is, mixing the refined fatty acid methyl esters and palm oil and then pumping them into the chlorination reaction tower for chlorination reaction.
  • the specific chlorination is The reaction temperature is consistent with the above-mentioned scheme, and will not be repeated here.
  • the mass ratio of the refined fatty acid methyl ester to palm oil is preferably (1-9):1, more preferably (3-8):1.
  • palm oil is added to increase the average molecular weight of the final plasticizer product and the viscosity of the product.
  • the prepared chlorinated fatty acid ester environmentally friendly plasticizer can meet the needs of different downstream customers.
  • the viscosity of the plasticizer is better, which is conducive to uniform mixing.
  • the viscosity of the plasticizer needs to be increased appropriately to avoid uneven material caused by sedimentation.
  • the specific viscosity is based on experience. Just choose, and there is no specific limitation here.
  • the present invention preferably controls the end point of the reaction by controlling the density of the product; in the present invention, when palm oil is not added in step (3), the density of the chlorinated material at the end of the chlorination reaction is preferably 1.06 to 1.25 g/cm 3 ; When palm oil is added in step (3), the density of the chlorinated material at the end of the chlorination reaction is preferably 1.06 to 1.18 g/cm 3 .
  • the composition of the obtained chlorinated material is methyl chlorinated fatty acid; when palm oil is added in step (3), the chlorinated material obtained is methyl chlorinated fatty acid A mixture of esters and chlorinated palm oil; in the present invention, it is preferred that during the production process, samples are taken to test the density of the product to determine the end point of the reaction.
  • the density of the chlorinated material there is a corresponding relationship between the density of the chlorinated material and the chlorine content.
  • the chlorine content of the chlorinated material with a density of 1.06g/cm 3 is about 25%; the chlorine content of chlorinated materials with a density of 1.25g/cm 3 is about 45%; when a mixture of fatty acid methyl ester and palm oil is used for chlorination, the chlorine content of chlorinated materials with a density of 1.06g/cm 3
  • the chlorine content of the chlorinated materials with a content of 23-25% and a density of 1.25g/cm 3 is 42-45%; when the density is the same, the viscosity of the chlorinated materials obtained after adding palm oil increases, the chlorine content decreases, and the average molecular weight
  • the viscosity, chlorine content and average molecular weight of the chlorinated material can be adjusted according to actual needs.
  • the present invention preferably stops the introduction of chlorine gas, and transfers the chlorinated material to the degassing tower while it is hot for degassing; in the present invention, the degassing is specifically: to the degassing tower Compressed air or nitrogen is blown into the system to remove chlorine and hydrogen chloride gas.
  • the degassing temperature is preferably 60-90°C, more preferably 70-80°C, when the acid value of the material to be chlorinated is ⁇ 0.5mgKOH/g , Stop swelling.
  • the present invention preferably mixes the degassed chlorinated material with the stabilizer to obtain the chlorinated fatty acid ester environmentally friendly plasticizer.
  • the stabilizer is preferably composed of ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent, and the ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, cyclic
  • the mass ratio of oxygenated soybean oil and anti-ultraviolet agent is preferably 1:(0-20):(0-20):(0.05 ⁇ 0.1); the added amount of the stabilizer is preferably 0.3-3% of the mass of the chlorinated material
  • the present invention has no special requirements on the type and source of the anti-ultraviolet agent, and a commercially available anti-ultraviolet agent well known to those skilled in the art can be used, specifically such as UV531, UV9000, UV326, etc.; The invention avoids the decomposition of the chloride
  • the invention also provides an environmentally friendly chlorinated fatty acid ester plasticizer prepared by the preparation method described in the above scheme.
  • the chlorinated fatty acid ester environmentally friendly plasticizer product provided by the invention has stable quality, non-toxicity, and excellent performance, and can prepare a series of products with different densities by controlling the reaction end point to meet the needs of different application fields.
  • the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 0.3wt% of the chlorinated material
  • the compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.06 to 1.09 g/cm 3.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:20:0:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:20:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:10:10:0.06.
  • the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 0.3wt% of the chlorinated material
  • the compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.06 to 1.09 g/cm 3.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:20:0:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:20:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:10:10:0.06.
  • the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 0.3wt% of the chlorinated material
  • the compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.06 to 1.09 g/cm 3.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:20:0:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:20:0.06.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
  • the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:10:10:0.06.
  • the stability of the obtained plasticizer was tested.
  • the obtained plasticizer was placed in a dry, sealed, and room temperature condition for 180 days, and the chromaticity and heating loss of the plasticizer before and after placement were tested (heated at 125°C for 2h, test The difference in quality after heating and before heating), acid value, density and thermal decomposition temperature.
  • the comparative test results of the plasticizer sample (recorded as 1-1 sample) obtained in (1-1) in Example 1 are shown in Table 1. Show:
  • the other plasticizer samples obtained in Examples 1 to 3 were subjected to the same stability test.
  • the test results showed that the obtained plasticizer was stored for 180 days under dry, sealed, and normal temperature conditions, and the performance of the product was basically unchanged, indicating the present invention
  • the prepared plasticizer has high quality stability.
  • Example 2 In parts by mass, take 50 parts of each of the plasticizer sample and DOTP (dioctyl terephthalate) obtained in Example 1 (1-1), add 100 parts of PVC resin powder and 2 parts of calcium zinc stabilizer, respectively, 0.5 part of stearic acid was mixed uniformly, and then smelted in a two-roll mill. After the smelted, it was vulcanized on a flat vulcanizer to make PVC plastic products; the properties of the products were tested, and the results are shown in Table 2:

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Abstract

The present invention relates to the technical field of plasticizers, and provides a chlorinated fatty acid ester environment-friendly plasticizer and a preparation method therefor. In the present invention, palm oil is used for preparing fatty acid methyl ester, refined fatty acid methyl ester is chlorinated and then mixed with a stabilizer, and the chlorinated fatty acid ester environment-friendly plasticizer in the present invention is obtained. The palm oil is natural oil, resources are rich, components are stable, the costs are low, and the prepared plasticizer product is stable in quality and non-toxic; furthermore, in the present invention, the refined fatty acid methyl ester can be directly chlorinated or mixed with palm oil and then chlorinated, and the end point of the chlorination reaction is controlled according to density requirements, so that a series of chlorinated fatty acid ester environment-friendly plasticizers having different densities are obtained. The whole reaction process of the preparation method provided in the present invention is easily controlled, the production process is environmentally friendly and economical, the operation is simple, and the preparation method is suitable for large-scale industrial production.

Description

一种氯代脂肪酸酯环保增塑剂及其制备方法Environmental protection plasticizer of chlorinated fatty acid ester and preparation method thereof
本申请要求于2020年4月20日提交中国专利局、申请号为202010310925.1、发明名称为“一种氯代脂肪酸酯环保增塑剂及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on April 20, 2020, the application number is 202010310925.1, and the invention title is "A chlorinated fatty acid ester environmentally friendly plasticizer and its preparation method", all of which The content is incorporated in this application by reference.
技术领域Technical field
本发明涉及增塑剂技术领域，特别涉及一种氯代脂肪酸酯环保增塑剂及其制备方法。The invention relates to the technical field of plasticizers, in particular to a chlorinated fatty acid ester environmentally friendly plasticizer and a preparation method thereof.
背景技术Background technique
增塑剂是在塑料、橡胶等制品加工过程中最重要的化学助剂。增塑剂种类繁多，其中以邻苯二甲酸酯(丁酯、辛酯)应用最为普遍。随着人类环保意识的增强，增塑剂的毒性越来越受到人们的重视，传统的邻苯二甲酸酯类增塑剂因有致癌嫌疑在国外的许多领域被禁用。Plasticizers are the most important chemical additives in the processing of plastics, rubber and other products. There are many types of plasticizers, among which phthalates (butyl ester and octyl ester) are the most commonly used. With the enhancement of human environmental protection awareness, the toxicity of plasticizers has attracted more and more attention. Traditional phthalate plasticizers have been banned in many fields abroad due to the suspected carcinogenicity.
随着环保意识的增强，人们越来越关注植物油基增塑剂的应用及加工。长期以来，植物油基增塑剂主要以环氧类产品为主，其在生产加工过程中产生大量的三废，限制其产业的发展。氯代脂肪酸酯是一种以油脂为原料开发的环保增塑剂，但目前的氯代脂肪酸酯产品一般以地沟油、泔水油等废弃油脂及酸化油为原料，制备过程难以控制，产品质量不稳定。With the increasing awareness of environmental protection, people are paying more and more attention to the application and processing of vegetable oil-based plasticizers. For a long time, vegetable oil-based plasticizers are mainly epoxy products, which produce a large amount of three wastes in the production and processing process, which restricts the development of its industry. Chlorinated fatty acid ester is an environmentally friendly plasticizer developed with oil as raw material, but current chlorinated fatty acid ester products generally use waste oil and acidified oil such as waste oil and swill oil as raw materials, and the preparation process is difficult to control. The quality is unstable.
发明内容Summary of the invention
本发明目的在于提供一种氯代脂肪酸酯环保增塑剂及其制备方法。本发明提供的制备方法以棕榈油为原料制备氯代脂肪酸酯环保增塑剂，整个制备过程容易控制，产品质量稳定，无毒。The purpose of the present invention is to provide an environmentally friendly plasticizer for chlorinated fatty acid esters and a preparation method thereof. The preparation method provided by the invention uses palm oil as a raw material to prepare a chlorinated fatty acid ester environmentally friendly plasticizer, the entire preparation process is easy to control, and the product quality is stable and non-toxic.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
一种氯代脂肪酸酯环保增塑剂的制备方法，包括以下步骤：A preparation method of chlorinated fatty acid ester environmental protection plasticizer, including the following steps:
(1)将棕榈油、甲醇和甲醇钠甲醇溶液混合进行酯交换反应，得到粗脂肪酸甲酯；(1) Mixing palm oil, methanol and sodium methoxide methanol solution for transesterification to obtain crude fatty acid methyl ester;
(2)将所述粗脂肪酸甲酯进行精馏，得到精制脂肪酸甲酯；(2) rectifying the crude fatty acid methyl esters to obtain refined fatty acid methyl esters;
(3)在氯气条件下，将所述精制脂肪酸甲酯进行氯化反应，得到氯代物料；(3) Under chlorine conditions, subject the refined fatty acid methyl esters to a chlorination reaction to obtain chlorinated materials;
(4)将所述氯代物料和稳定剂混合，得到氯代脂肪酸酯环保增塑剂。(4) Mixing the chlorinated material and the stabilizer to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester.
优选的，所述酯交换反应的温度为65～75℃，时间为0.5～1.5h；Preferably, the temperature of the transesterification reaction is 65-75°C, and the time is 0.5-1.5h;
所述棕榈油的酸值≤0.6mgKOH/g，水分含量≤0.15wt％，碘值为15～38；所述甲醇钠甲醇溶液中甲醇钠的质量百分含量为27.0～31.0％；The acid value of the palm oil is ≤0.6mgKOH/g, the moisture content is ≤0.15wt%, and the iodine value is 15-38; the mass percentage of sodium methoxide in the sodium methoxide methanol solution is 27.0-31.0%;
以棕榈油、甲醇和甲醇钠甲醇溶液的总质量为100％计，所述棕榈油的质量百分含量为85.0～86.4％，甲醇的质量百分含量为12.9～14.2％，甲醇钠甲醇溶液的质量百分含量为0.6～0.9％。Based on the total mass of palm oil, methanol and sodium methoxide methanol solution as 100%, the mass percentage of palm oil is 85.0-86.4%, the mass percentage of methanol is 12.9-14.2%, and the sodium methoxide methanol solution is The mass percentage content is 0.6 to 0.9%.
优选的，所述精馏的真空度为-0.09～-0.095Mpa，回流比为0～2，塔底温度为220～240℃，塔顶温度为170～200℃，塔板数为25～30。Preferably, the vacuum degree of the rectification is -0.09～-0.095Mpa, the reflux ratio is 0～2, the bottom temperature is 220～240℃, the top temperature is 170～200℃, and the number of plates is 25～30. .
优选的，所述氯化反应的温度为85～115℃。Preferably, the temperature of the chlorination reaction is 85-115°C.
优选的，所述步骤(3)中，在氯化反应前，还包括将精制脂肪酸甲酯和棕榈油混合；所述精制脂肪酸甲酯和棕榈油的质量比为(1～9):1。Preferably, in the step (3), before the chlorination reaction, it further includes mixing refined fatty acid methyl esters and palm oil; the mass ratio of the refined fatty acid methyl esters to palm oil is (1-9):1.
优选的，当所述步骤(3)中不加入棕榈油时，所述氯化反应的终点的氯代物料密度为1.06～1.25g/cm 3。 Preferably, when palm oil is not added in the step (3), the density of the chlorinated material at the end of the chlorination reaction is 1.06-1.25 g/cm 3 .
优选的，当所述步骤(3)中加入棕榈油时，所述氯化反应的终点的氯代物料密度为1.06～1.18g/cm 3。 Preferably, when palm oil is added in the step (3), the density of the chlorinated material at the end of the chlorination reaction is 1.06 to 1.18 g/cm 3 .
优选的，所述氯代物料与稳定剂混合前还包括：将所述氯代物料进行脱气，所述脱气的温度为60～90℃，脱气至氯代物料的酸值≤0.5mgKOH/g。Preferably, before mixing the chlorinated material with the stabilizer, it further includes: degassing the chlorinated material, the temperature of the degassing is 60-90°C, and the degassing until the acid value of the chlorinated material is ≤0.5mgKOH /g.
优选的，所述稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂组成，所述乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂的质量比为1:(0～20):(0～20):(0.05～0.1)；Preferably, the stabilizer is composed of ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxidized soybean oil, and an anti-ultraviolet agent, and the ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil The mass ratio with the anti-ultraviolet agent is 1:(0～20):(0～20):(0.05～0.1);
所述稳定剂的加入量为氯代物料质量的0.3～3％。The added amount of the stabilizer is 0.3-3% of the mass of the chlorinated material.
本发明还提供了上述方案所述制备方法制备的氯代脂肪酸酯环保增塑剂。The invention also provides an environmentally friendly chlorinated fatty acid ester plasticizer prepared by the preparation method described in the above scheme.
本发明提供了一种氯代脂肪酸酯环保增塑剂的制备方法，本发明利用棕榈油制备脂肪酸甲酯，将精制脂肪酸甲酯氯化后和稳定剂混合，得到本发明的氯代脂肪酸酯环保增塑剂。棕榈油为天然油脂，资源丰富，成分稳定，成本低，制备得到的增塑剂产品质量稳定，无毒，并且由于棕榈油成分稳定，本发明的整个制备过程更加容易控制；进一步的，本发明可以选择将精制脂肪酸甲酯直接氯化或和棕榈油混合后再进行氯化，根据密度需 求控制氯化反应的终点，从而得到不同密度的一系列氯代脂肪酸酯环保增塑剂。本发明提供的制备方法整个反应过程容易控制，生产工艺既环保又经济，操作简单，适合于大规模工业化生产。The present invention provides a method for preparing a chlorinated fatty acid ester environmentally friendly plasticizer. The present invention uses palm oil to prepare fatty acid methyl esters, and mixes the refined fatty acid methyl esters with a stabilizer after chlorination to obtain the chlorinated fatty acid of the present invention Ester environmentally friendly plasticizer. Palm oil is a natural fat, rich in resources, stable in ingredients, and low in cost. The prepared plasticizer product is stable in quality and non-toxic. Because of the stable ingredients in palm oil, the entire preparation process of the present invention is easier to control; further, the present invention You can choose to directly chlorinate the refined fatty acid methyl ester or mix it with palm oil before chlorination, and control the end point of the chlorination reaction according to the density requirement, so as to obtain a series of environmentally friendly chlorinated fatty acid ester plasticizers with different densities. The preparation method provided by the invention is easy to control the entire reaction process, the production process is environmentally friendly and economical, and the operation is simple, which is suitable for large-scale industrial production.
本发明还提供了上述方案所述制备方法制备的氯代脂肪酸酯环保增塑剂。本发明提供的氯代脂肪酸酯环保增塑剂产品质量稳定，不含重金属和邻苯类物质，与PVC相容性良好，具有优良的阻燃、环保性能，且价格低廉，可广泛用于薄膜、人造革、塑料地板、电线电缆护套等PVC领域，还可以替代氯化石蜡应用于聚氨酯领域。实施例结果表明，以本发明的氯代脂肪酸酯环保增塑剂制备PVC制品，所得制品的性能和以对苯二甲酸二辛酯为增塑剂制备的PVC制品性能相似，说明本发明的氯代脂肪酸酯环保增塑剂可以代替对苯二甲酸二辛酯，是一种理想的环保增塑剂。The invention also provides an environmentally friendly chlorinated fatty acid ester plasticizer prepared by the preparation method described in the above scheme. The chlorinated fatty acid ester environmental protection plasticizer product provided by the invention has stable quality, does not contain heavy metals and o-benzene substances, has good compatibility with PVC, has excellent flame retardant and environmental protection performance, and is low in price. It can be widely used Films, artificial leather, plastic floors, wire and cable sheaths and other PVC fields can also replace chlorinated paraffin in the polyurethane field. The results of the examples show that the performance of the PVC products prepared with the environmentally friendly chlorinated fatty acid ester plasticizer of the present invention is similar to that of the PVC products prepared with dioctyl terephthalate as the plasticizer, indicating the performance of the present invention Chlorinated fatty acid ester environmental protection plasticizer can replace dioctyl terephthalate and is an ideal environmental protection plasticizer.
具体实施方式Detailed ways
下面结合实施例和附图对本发明进行进一步说明。The present invention will be further described below in conjunction with embodiments and drawings.
本发明提供了一种氯代脂肪酸酯环保增塑剂的制备方法，包括以下步骤：The invention provides a preparation method of a chlorinated fatty acid ester environmentally friendly plasticizer, which comprises the following steps:
(1)将棕榈油、甲醇和甲醇钠甲醇溶液混合进行酯交换反应，得到粗脂肪酸甲酯；(1) Mixing palm oil, methanol and sodium methoxide methanol solution for transesterification to obtain crude fatty acid methyl ester;
(2)将所述粗脂肪酸甲酯进行精馏，得到精制脂肪酸甲酯；(2) rectifying the crude fatty acid methyl esters to obtain refined fatty acid methyl esters;
(3)在氯气条件下，将所述精制脂肪酸甲酯进行氯化反应，得到氯代物料；(3) Under chlorine conditions, subject the refined fatty acid methyl esters to a chlorination reaction to obtain chlorinated materials;
(4)将所述氯代物料和稳定剂混合，得到氯代脂肪酸酯环保增塑剂。(4) Mixing the chlorinated material and the stabilizer to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester.
本发明将棕榈油、甲醇和甲醇钠甲醇溶液混合进行酯交换反应，得到粗脂肪酸甲酯。在本发明中，所述棕榈油的酸值优选≤0.6mgKOH/g，更优选为0.1～0.5mgKOH/g，水分含量优选≤0.15wt％，更优选为0.05～0.1wt％，碘值优选为15～38，更优选为20～35；所述甲醇的纯度优选≥99.0％；所述甲醇钠甲醇溶液中甲醇钠的质量百分含量优选为27.0～31.0％，更优选为28.0～30.0％。在本发明的具体实施例中，直接使用市售的甲醇钠甲醇溶液进行配料即可。In the present invention, palm oil, methanol and sodium methoxide methanol solution are mixed for transesterification reaction to obtain crude fatty acid methyl ester. In the present invention, the acid value of the palm oil is preferably ≤ 0.6 mgKOH/g, more preferably 0.1 to 0.5 mgKOH/g, the moisture content is preferably ≤ 0.15 wt%, more preferably 0.05 to 0.1 wt%, and the iodine value is preferably 15-38, more preferably 20-35; the purity of the methanol is preferably ≥99.0%; the mass percentage of sodium methoxide in the sodium methoxide methanol solution is preferably 27.0-31.0%, more preferably 28.0-30.0%. In the specific embodiment of the present invention, a commercially available methanol solution of sodium methoxide can be used directly for dosing.
在本发明中，以棕榈油、甲醇和甲醇钠甲醇溶液的总质量为100％计，所述棕榈油的质量百分含量优选为85.0～86.4％，更优选为85.5～86％，所 述甲醇的质量百分含量优选为12.9～14.2％，更优选为13～14％，本发明所述的甲醇的质量百分含量不包括甲醇钠甲醇溶液中引入的甲醇，所述甲醇钠甲醇溶液的质量百分含量优选为0.6～0.9％，更优选为0.7～0.8％。In the present invention, based on the total mass of palm oil, methanol and sodium methoxide methanol solution as 100%, the mass percentage of the palm oil is preferably 85.0-86.4%, more preferably 85.5-16%. The mass percentage of the methanol is preferably 12.9 to 14.2%, more preferably 13 to 14%. The mass percentage of methanol in the present invention does not include the methanol introduced in the sodium methoxide methanol solution, and the mass of the sodium methoxide methanol solution The percentage content is preferably 0.6 to 0.9%, more preferably 0.7 to 0.8%.
在本发明中，所述酯交换反应的温度优选为65～75℃，更优选为68～72℃，所述酯交换反应的时间优选为0.5～1.5h，更优选为1h。在本发明中，所述酯交换反应优选在酯交换反应釜中进行，本发明优选将棕榈油预热至60℃后投入酯交换反应釜中，然后再依次加入甲醇和甲醇钠甲醇溶液。在酯交换反应过程中，棕榈油和甲醇在甲醇钠的催化作用下发生酯交换反应，生成脂肪酸甲酯和甘油。In the present invention, the temperature of the transesterification reaction is preferably 65-75°C, more preferably 68-72°C, and the time of the transesterification reaction is preferably 0.5-1.5 h, more preferably 1 h. In the present invention, the transesterification reaction is preferably carried out in a transesterification reactor. In the present invention, palm oil is preferably preheated to 60° C. and then put into the transesterification reactor, and then methanol and sodium methoxide methanol solution are sequentially added. During the transesterification reaction, palm oil and methanol undergo transesterification under the catalysis of sodium methoxide to generate fatty acid methyl esters and glycerin.
在本发明中，所述酯交换反应的产物为脂肪酸甲酯和甘油的混合物；本发明优选通过后处理从酯交换反应产物中分离出粗脂肪酸甲酯；所述后处理优选包括以下步骤：将所得酯交换反应产物静置分层后排出下层的粗甘油，将剩余物料进行减压蒸馏，得到粗脂肪酸甲酯。在本发明中，所述减压蒸馏的真空度优选为-0.06～-0.09MPa，所述减压蒸馏的温度优选为60～90℃；本发明通过减压蒸馏回收甲醇并将甲醇进行循环利用。In the present invention, the product of the transesterification reaction is a mixture of fatty acid methyl esters and glycerol; in the present invention, crude fatty acid methyl esters are preferably separated from the transesterification reaction product through post-treatment; the post-treatment preferably includes the following steps: After the obtained transesterification reaction product is allowed to stand for stratification, the crude glycerin in the lower layer is discharged, and the remaining materials are subjected to vacuum distillation to obtain crude fatty acid methyl esters. In the present invention, the vacuum degree of the vacuum distillation is preferably -0.06 to -0.09 MPa, and the temperature of the vacuum distillation is preferably 60 to 90°C; the present invention recovers methanol through vacuum distillation and recycles the methanol. .
得到粗脂肪酸甲酯后，本发明将所述粗脂肪酸甲酯进行精馏，得到精制脂肪酸甲酯。在本发明中，所述精馏优选在精馏塔中进行，所述精馏的真空度优选为-0.09～-0.095Mpa，回流比优选为0～2，更优选为1～2，塔板数优选为25～30，塔底温度优选为220～240℃，更优选为225～235℃，塔顶温度优选为170～200℃，更优选为180～190℃；本发明通过精馏塔分流从塔顶得到精制脂肪酸甲酯，塔底为反应不完全的釜残；本发明精制脂肪酸甲酯的得率≥96.5％。本发明通过精馏可以得到精制脂肪酸甲酯，避免反应不完全的物料参加后续的氯化反应，反应不完全的物料中存在甲酯、单甘脂、二甘酯等，其中的羟基会严重影响产品的应用性能。After obtaining crude fatty acid methyl esters, the present invention rectifies the crude fatty acid methyl esters to obtain refined fatty acid methyl esters. In the present invention, the rectification is preferably carried out in a rectification tower. The vacuum degree of the rectification is preferably -0.09～-0.095Mpa, and the reflux ratio is preferably 0-2, more preferably 1-2. The number is preferably 25 to 30, the bottom temperature is preferably 220 to 240°C, more preferably 225 to 235°C, and the top temperature is preferably 170 to 200°C, more preferably 180 to 190°C; the present invention divides the flow through the rectification tower The refined fatty acid methyl ester is obtained from the top of the tower, and the bottom of the tower is the still residue with incomplete reaction; the yield of the refined fatty acid methyl ester of the present invention is greater than or equal to 96.5%. In the present invention, refined fatty acid methyl esters can be obtained through rectification, and the incompletely reacted materials can be prevented from participating in the subsequent chlorination reaction. There are methyl esters, monoglycerides, diglycerides, etc. in the incompletely reacted materials, and the hydroxyl groups in them will seriously affect The application performance of the product.
得到精制脂肪酸甲酯后，本发明在氯气条件下，将所述精制脂肪酸甲酯进行氯化反应，得到氯代物料。在本发明中，所述氯化反应的温度优选为85～115℃，更优选为90～110℃；所述氯化反应优选在氯化反应塔中进行；本发明优选将精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度为85～115℃。After the refined fatty acid methyl ester is obtained, in the present invention, the refined fatty acid methyl ester is subjected to a chlorination reaction under the condition of chlorine gas to obtain a chlorinated material. In the present invention, the temperature of the chlorination reaction is preferably 85-115°C, more preferably 90-110°C; the chlorination reaction is preferably carried out in a chlorination reaction tower; in the present invention, the refined fatty acid methyl ester is preferably beaten Enter the chlorination reaction tower, turn on the circulating pump, pass in chlorine gas, control the circulating water flow of the condenser, and maintain the reaction temperature at 85-115°C.
在本发明中，所述氯化反应前优选还包括将精制脂肪酸甲酯和棕榈油 混合，即将精制脂肪酸甲酯和棕榈油混合后打入氯化反应塔中进行氯化反应，具体的氯化反应温度和上述方案一致，在此不再赘述。在本发明中，所述精制脂肪酸甲酯和棕榈油的质量比优选为(1～9):1，更优选为(3～8):1。本发明通过加入棕榈油增加最终所得增塑剂成品的平均分子量，增加产品的粘度，制备出来的氯代脂肪酸酯环保增塑剂能够满足不同下游客户的需求，比如在本发明的具体实施例中，制备普通PVC树脂时增塑剂的粘度较小为好，有利于混合均匀，制备PVC糊树脂时，增塑剂的粘度需要适当增大，避免沉降造成物料不均，具体粘度根据经验进行选择即可，在此不做具体限定。In the present invention, the chlorination reaction preferably further includes mixing refined fatty acid methyl esters and palm oil, that is, mixing the refined fatty acid methyl esters and palm oil and then pumping them into the chlorination reaction tower for chlorination reaction. The specific chlorination is The reaction temperature is consistent with the above-mentioned scheme, and will not be repeated here. In the present invention, the mass ratio of the refined fatty acid methyl ester to palm oil is preferably (1-9):1, more preferably (3-8):1. In the present invention, palm oil is added to increase the average molecular weight of the final plasticizer product and the viscosity of the product. The prepared chlorinated fatty acid ester environmentally friendly plasticizer can meet the needs of different downstream customers. For example, in the specific embodiment of the present invention In the preparation of ordinary PVC resin, the viscosity of the plasticizer is better, which is conducive to uniform mixing. When preparing PVC paste resin, the viscosity of the plasticizer needs to be increased appropriately to avoid uneven material caused by sedimentation. The specific viscosity is based on experience. Just choose, and there is no specific limitation here.
本发明优选通过控制产品的密度，控制反应终点；在本发明中，当步骤(3)中不加入棕榈油时，所述氯化反应的终点的氯代物料密度优选为1.06～1.25g/cm 3；当步骤(3)中加入棕榈油时，所述氯化反应的终点的氯代物料密度优选为1.06～1.18g/cm 3。在本发明中，当步骤(3)中不加入棕榈油时，所得氯代物料的成分为氯代脂肪酸甲酯；当步骤(3)中加入棕榈油时，所得氯代物料为氯代脂肪酸甲酯和氯代棕榈油的混合物；本发明优选在生产过程中，取样测试产物的密度，以确定反应终点。 The present invention preferably controls the end point of the reaction by controlling the density of the product; in the present invention, when palm oil is not added in step (3), the density of the chlorinated material at the end of the chlorination reaction is preferably 1.06 to 1.25 g/cm 3 ; When palm oil is added in step (3), the density of the chlorinated material at the end of the chlorination reaction is preferably 1.06 to 1.18 g/cm 3 . In the present invention, when palm oil is not added in step (3), the composition of the obtained chlorinated material is methyl chlorinated fatty acid; when palm oil is added in step (3), the chlorinated material obtained is methyl chlorinated fatty acid A mixture of esters and chlorinated palm oil; in the present invention, it is preferred that during the production process, samples are taken to test the density of the product to determine the end point of the reaction.
在本发明中，氯代物料密度与氯含量存在对应关系，当采用精制脂肪酸甲酯(不加入棕榈油)进行氯化反应时，密度为1.06g/cm 3的氯代物料的氯含量约为25％；密度为1.25g/cm 3的氯代物料的氯含量约为45％；当采用脂肪酸甲酯和棕榈油混合进行氯化反应时，密度为1.06g/cm 3的氯代物料的氯含量为23～25％，密度1.25g/cm 3的氯代物料的氯含量为42～45％；密度相同的情况下，加入棕榈油后所得氯代物料的粘度增加、氯含量降低，平均分子量增加，在本发明的具体实施例中，可以根据实际需求对氯代物料的粘度、氯含量和平均分子量进行调节。 In the present invention, there is a corresponding relationship between the density of the chlorinated material and the chlorine content. When the refined fatty acid methyl ester (without palm oil) is used for the chlorination reaction, the chlorine content of the chlorinated material with a density of 1.06g/cm 3 is about 25%; the chlorine content of chlorinated materials with a density of 1.25g/cm 3 is about 45%; when a mixture of fatty acid methyl ester and palm oil is used for chlorination, the chlorine content of chlorinated materials with a density of 1.06g/cm 3 The chlorine content of the chlorinated materials with a content of 23-25% and a density of 1.25g/cm 3 is 42-45%; when the density is the same, the viscosity of the chlorinated materials obtained after adding palm oil increases, the chlorine content decreases, and the average molecular weight In addition, in the specific embodiment of the present invention, the viscosity, chlorine content and average molecular weight of the chlorinated material can be adjusted according to actual needs.
反应达到设定的物料密度后，本发明优选停止通入氯气，将氯代物料趁热转移至脱气塔中进行脱气；在本发明中，所述脱气具体为：向脱气塔中鼓入压缩空气或氮气，去除体系中的氯气及氯化氢气体，所述脱气的温度优选为60～90℃，更优选为70～80℃，待氯代物料的酸值≤0.5mgKOH/g时，停止鼓气。After the reaction reaches the set material density, the present invention preferably stops the introduction of chlorine gas, and transfers the chlorinated material to the degassing tower while it is hot for degassing; in the present invention, the degassing is specifically: to the degassing tower Compressed air or nitrogen is blown into the system to remove chlorine and hydrogen chloride gas. The degassing temperature is preferably 60-90°C, more preferably 70-80°C, when the acid value of the material to be chlorinated is ≤0.5mgKOH/g , Stop swelling.
脱气完成后，本发明优选将脱气后的氯代物料和稳定剂混合，得到氯 代脂肪酸酯环保增塑剂。在本发明中，所述稳定剂优选由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂组成，所述乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂的质量比优选为1:(0～20):(0～20):(0.05～0.1)；所述稳定剂的加入量优选为氯代物料质量的0.3～3％；本发明对所述抗紫外剂的种类和来源没有特殊要求，使用本领域技术人员熟知的市售抗紫外剂即可，具体的如UV531，UV9000、UV326等。本发明通过加入稳定剂避免氯代脂肪酸酯的分解，提高增塑剂的稳定性，使增塑剂能够长期保存。After the degassing is completed, the present invention preferably mixes the degassed chlorinated material with the stabilizer to obtain the chlorinated fatty acid ester environmentally friendly plasticizer. In the present invention, the stabilizer is preferably composed of ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent, and the ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, cyclic The mass ratio of oxygenated soybean oil and anti-ultraviolet agent is preferably 1:(0-20):(0-20):(0.05～0.1); the added amount of the stabilizer is preferably 0.3-3% of the mass of the chlorinated material The present invention has no special requirements on the type and source of the anti-ultraviolet agent, and a commercially available anti-ultraviolet agent well known to those skilled in the art can be used, specifically such as UV531, UV9000, UV326, etc.; The invention avoids the decomposition of the chlorinated fatty acid ester by adding a stabilizer, improves the stability of the plasticizer, and enables the plasticizer to be stored for a long time.
本发明还提供了上述方案所述制备方法制备的氯代脂肪酸酯环保增塑剂。本发明提供的氯代脂肪酸酯环保增塑剂产品质量稳定、无毒、性能优异，且可以通过控制反应终点制备得到不同密度的一系列产品，满足不同应用领域的需求。The invention also provides an environmentally friendly chlorinated fatty acid ester plasticizer prepared by the preparation method described in the above scheme. The chlorinated fatty acid ester environmentally friendly plasticizer product provided by the invention has stable quality, non-toxicity, and excellent performance, and can prepare a series of products with different densities by controlling the reaction end point to meet the needs of different application fields.
下面结合实施例对本发明提供的方案进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The solutions provided by the present invention will be described in detail below in conjunction with the examples, but they should not be understood as limiting the protection scope of the present invention.
实施例1Example 1
将85wt％的棕榈油(酸值0.58mgKOH/g，水分0.15wt％，碘值38)，预热至60℃投入酯交换反应釜中，再依次投入14.2wt％的甲醇(纯度99.2％)和0.8wt％的甲醇钠甲醇溶液(甲醇钠质量百分含量27.1wt％)，加热至70±5℃反应1h，静置1h分出下层粗甘油，上层含甲醇的脂肪酸甲酯减压蒸馏除掉甲醇，减压蒸馏的真空度-0.06～-0.09MPa，温度60～90℃；除掉甲醇的粗脂肪酸甲酯送入精馏塔中进行提纯，真空度-0.09～-0.095Mpa，回流比0～2，塔底温度220～240℃，塔顶温度170～200℃；经过精馏塔分流从塔顶得到精制脂肪酸甲酯，塔底为反应不完全的釜残。通过控制粗脂肪酸甲酯进入精馏塔的量与塔底釜残排除量，达到精制脂肪酸甲酯得率96.5％。Put 85wt% palm oil (acid value 0.58mgKOH/g, moisture 0.15wt%, iodine value 38), preheated to 60℃ and put it into the transesterification reactor, and then put 14.2wt% methanol (purity 99.2%) and 0.8wt% sodium methoxide methanol solution (sodium methoxide mass percentage 27.1wt%), heated to 70±5℃ and reacted for 1h, let stand for 1h to separate the crude glycerin from the lower layer, and the fatty acid methyl ester containing methanol in the upper layer was removed by vacuum distillation Methanol, vacuum degree of vacuum distillation -0.06～-0.09MPa, temperature 60～90℃; crude fatty acid methyl esters from methanol are sent to rectification tower for purification, vacuum degree -0.09～-0.095Mpa, reflux ratio 0 ～2, the temperature at the bottom of the tower is 220-240°C, and the temperature at the top of the tower is 170-200°C; the refined fatty acid methyl ester is obtained from the top of the rectification tower through the split flow of the rectification tower, and the bottom of the tower is the residue with incomplete reaction. By controlling the amount of crude fatty acid methyl ester entering the rectification tower and the amount of residue from the bottom of the tower, the yield of refined fatty acid methyl ester is 96.5%.
利用所得精制脂肪酸甲酯进行后续增塑剂的制备，具体如下：Use the obtained refined fatty acid methyl ester to prepare the subsequent plasticizer, specifically as follows:
(1-1)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.06～1.09g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯 代物料0.3wt％的复合稳定剂，混合均匀，得到密度为1.06～1.09g/cm 3的氯代脂肪酸酯环保增塑剂。 (1-1) The refined fatty acid methyl ester is pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.06 to 1.09g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot. Blow in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 0.3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.06 to 1.09 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：0：0.05混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
或：or:
(1-2)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.09～1.18g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，混合均匀得到密度为1.09～1.18g/cm 3的氯代脂肪酸酯环保增塑剂。 (1-2) Refined fatty acid methyl esters are pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.09-1.18g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60-90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.09 to 1.18 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：20：0：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:20:0:0.06.
或：or:
(1-3)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.18～1.25g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，混合均匀得到密度为1.18～1.25g/cm 3的氯代脂肪酸酯环保增塑剂。 (1-3) Refined fatty acid methyl esters are pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.18-1.25g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60-90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.18-1.25 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：20：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:20:0.06.
或：or:
(1-4)9质量份精制脂肪酸甲酯与1质量份棕榈油混合均匀打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.06～1.09g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料0.3wt％的复合稳定剂，得到密度为1.06～1.09g/cm 3的氯代脂肪酸酯环保增塑剂。 (1-4) Mix 9 parts by mass of refined fatty acid methyl esters and 1 part by mass of palm oil into the chlorination reaction tower, turn on the circulating pump, pass in chlorine gas, control the circulating water flow in the condenser, and maintain the reaction temperature at 85-115°C , The density reaches 1.06～1.09g/cm 3 , stop the chlorine gas and transfer the material to the degassing tower while it’s hot, bubbling in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop bubbling to obtain chlorine Substitute materials; adding a composite stabilizer that accounts for 0.3wt% of the chlorinated materials to obtain a chlorinated fatty acid ester environmentally friendly plasticizer with a density of 1.06 to 1.09 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：0：0.05混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
或：or:
(1-5)1质量份精制脂肪酸甲酯与1质量份棕榈油混合均匀打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.09～1.18g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，得到密度为1.09～1.18g/cm 3的氯代脂肪酸酯环保增塑剂。 (1-5) 1 part by mass of refined fatty acid methyl ester and 1 part by mass of palm oil are uniformly mixed and fed into the chlorination reaction tower, the circulating pump is turned on, chlorine gas is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C , The density reaches 1.09～1.18g/cm 3 , stop the chlorine gas and transfer the material to the degassing tower while it’s hot, bubbling in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop bubbling to obtain chlorine Substituting materials; adding a composite stabilizer accounting for 3wt% of the chlorinated materials to obtain a chlorinated fatty acid ester environmentally friendly plasticizer with a density of 1.09 to 1.18 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：10：10：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:10:10:0.06.
实施例2Example 2
将86.4wt％的棕榈油(酸值0.28mgKOH/g，水分0.12％，碘值26)，预热至60℃投入酯交换反应釜中，再依次投入13.0wt％的甲醇(纯度99.0％)和0.6wt％的甲醇钠甲醇溶液(甲醇钠含量31.0wt％)，加热至70±5℃反应1h，静置1h分出下层粗甘油，上层含甲醇的脂肪酸甲酯减压蒸馏除掉甲醇，减压蒸馏的真空度-0.06～-0.09MPa，温度60～90℃；除掉甲醇的粗脂肪酸甲酯送入精馏塔中进行提纯，真空度-0.09～-0.095Mpa，回流比0～2，塔底温度220～240℃，塔顶温度170～200℃；经过精馏塔分流从塔上得到精制脂肪酸甲酯，塔底为反应不完全的釜残。通过控制粗脂肪酸甲酯进入精馏塔的量与塔底釜残排除量，达到精制脂肪酸甲酯得率96.5％。86.4wt% palm oil (acid value 0.28mgKOH/g, water content 0.12%, iodine value 26), preheated to 60 ℃ into the transesterification reactor, and then 13.0wt% methanol (purity 99.0%) and 0.6wt% sodium methoxide methanol solution (sodium methoxide content 31.0wt%), heated to 70±5℃, reacted for 1h, let stand for 1h to separate the crude glycerin from the lower layer, The vacuum degree of pressure distillation is -0.06～-0.09MPa, the temperature is 60～90℃; the crude fatty acid methyl ester from which methanol is removed is sent to the rectification tower for purification, the vacuum degree is -0.09～-0.095Mpa, the reflux ratio is 0～2, The temperature at the bottom of the tower is 220-240°C, and the temperature at the top of the tower is 170-200°C; the refined fatty acid methyl ester is obtained from the tower through the fractionation of the rectification tower, and the bottom of the tower is the residue with incomplete reaction. By controlling the amount of crude fatty acid methyl ester entering the rectification tower and the amount of residue from the bottom of the tower, the yield of refined fatty acid methyl ester is 96.5%.
利用所得精制脂肪酸甲酯进行后续增塑剂的制备，具体如下：Use the obtained refined fatty acid methyl ester to prepare the subsequent plasticizer, specifically as follows:
(2-1)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.06～1.09g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料0.3wt％的复合稳定剂，混合均匀，得到密度为1.06～1.09g/cm 3的氯代脂肪酸酯环保增塑剂。 (2-1) The refined fatty acid methyl ester is pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.06 to 1.09g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot. Blow in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 0.3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.06 to 1.09 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：0：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.06.
或：or:
(2-2)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.09～1.18g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，混合均匀得到密度为1.09～1.18g/cm 3的氯代脂肪酸酯环保增塑剂。 (2-2) Refined fatty acid methyl esters are pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.09-1.18g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60-90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.09 to 1.18 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：20：0：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:20:0:0.06.
或：or:
(2-3)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.18～1.25g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，混合均匀得到密度为1.18～1.25g/cm 3的氯代脂肪酸酯环保增塑剂。 (2-3) Refined fatty acid methyl esters are pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.18-1.25g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60-90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.18-1.25 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：20：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:20:0.06.
或：or:
(2-4)4质量份精制脂肪酸甲酯与1质量份的棕榈油混合均匀打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.06～1.09g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料0.3wt％的复合稳定剂，得到密度为1.06～1.09g/cm 3的氯代脂肪酸酯环保增塑剂。 (2-4) 4 parts by mass of refined fatty acid methyl esters and 1 part by mass of palm oil are evenly mixed and fed into the chlorination reaction tower, the circulating pump is turned on, chlorine gas is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115 ℃, the density reaches 1.06～1.09g/cm 3 , stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop the gas Chlorinated materials; adding a composite stabilizer accounting for 0.3 wt% of the chlorinated materials to obtain an environmentally friendly plasticizer of chlorinated fatty acid esters with a density of 1.06 to 1.09 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：0：0.05混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
或：or:
(2-5)2质量份精制脂肪酸甲酯与1质量份的原料棕榈油混合均匀打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持 反应温度85～115℃，密度达到1.09～1.18g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，得到密度为1.09～1.18g/cm 3的氯代脂肪酸酯环保增塑剂。 (2-5) 2 parts by mass of refined fatty acid methyl esters and 1 part by mass of raw palm oil are evenly mixed into the chlorination reaction tower, the circulating pump is turned on, chlorine gas is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85~ 115℃, the density reaches 1.09～1.18g/cm 3 , stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop blowing, A chlorinated material is obtained; a composite stabilizer accounting for 3 wt% of the chlorinated material is added to obtain an environmentally friendly chlorinated fatty acid ester plasticizer with a density of 1.09 to 1.18 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：10：10：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:10:10:0.06.
实施例3Example 3
将86.2wt％的棕榈油(酸值0.18mgKOH/g，水分0.09％，碘值15)，预热至60℃投入酯交换反应釜中，再依次投入12.9wt％的甲醇(纯度99.5％)和0.9wt％的甲醇钠甲醇溶液(甲醇钠含量28.5wt％)，加热至70±5℃反应1h，静置1h分出下层粗甘油，上层含甲醇的脂肪酸甲酯减压蒸馏除掉甲醇，减压蒸馏真空度-0.06～-0.09MPa，温度60～90℃；除掉甲醇的粗脂肪酸甲酯送入精馏塔中进行提纯，真空度-0.09～-0.095Mpa，回流比0～2，塔底温度220～240℃，塔顶温度170～200℃；经过精馏塔分流从塔上得到精制脂肪酸甲酯，塔底为反应不完全的釜残。通过控制粗脂肪酸甲酯进入精馏塔的量与塔底釜残排除量，达到精制脂肪酸甲酯得率96.5％。Put 86.2wt% palm oil (acid value 0.18mgKOH/g, moisture 0.09%, iodine value 15), preheated to 60℃ and put it into the transesterification reactor, then put 12.9wt% methanol (purity 99.5%) and 0.9wt% sodium methoxide methanol solution (sodium methoxide content 28.5wt%), heated to 70±5℃ for 1h, let stand for 1h to separate the crude glycerin in the lower layer, and the fatty acid methyl ester containing methanol in the upper layer was distilled under reduced pressure to remove the methanol. Pressure distillation vacuum degree -0.06～-0.09MPa, temperature 60～90℃; crude fatty acid methyl ester from which methanol is removed is sent to rectification tower for purification, vacuum degree -0.09～-0.095Mpa, reflux ratio 0～2, tower The bottom temperature is 220-240°C, and the top temperature is 170-200°C; the refined fatty acid methyl ester is obtained from the tower through the fractionation of the rectification tower, and the bottom of the tower is the residue with incomplete reaction. By controlling the amount of crude fatty acid methyl ester entering the rectification tower and the amount of residue from the bottom of the tower, the yield of refined fatty acid methyl ester is 96.5%.
利用所得精制脂肪酸甲酯进行后续增塑剂的制备，具体如下：Use the obtained refined fatty acid methyl ester to prepare the subsequent plasticizer, specifically as follows:
(3-1)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.06～1.09g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料0.3wt％的复合稳定剂，混合均匀，得到密度为1.06～1.09g/cm 3的氯代脂肪酸酯环保增塑剂。 (3-1) The refined fatty acid methyl ester is pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.06 to 1.09g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot. Blow in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 0.3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.06 to 1.09 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：0：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.06.
或：or:
(3-2)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.09～1.18g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯 代物料3wt％的复合稳定剂，混合均匀得到密度为1.09～1.18g/cm 3的氯代脂肪酸酯环保增塑剂。 (3-2) Refined fatty acid methyl esters are pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.09-1.18g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60-90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.09 to 1.18 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：20：0：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:20:0:0.06.
或：or:
(3-3)精制脂肪酸甲酯打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.18～1.25g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，混合均匀得到密度为1.18～1.25g/cm 3的氯代脂肪酸酯环保增塑剂。 (3-3) Refined fatty acid methyl esters are pumped into the chlorination reaction tower, the circulating pump is turned on, chlorine is introduced, the circulating water flow of the condenser is controlled, and the reaction temperature is maintained at 85-115°C, and the density reaches 1.18-1.25g/cm 3 , Stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60-90℃, the acid value reaches 0.5mgKOH/g, stop the gas, and obtain the chlorinated material; add 3wt% of the chlorinated material The compound stabilizer is mixed uniformly to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester with a density of 1.18-1.25 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：20：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:20:0.06.
或：or:
(3-4)5质量份精制脂肪酸甲酯与1质量份棕榈油混合均匀打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.06～1.09g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60～90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料0.3wt％的复合稳定剂，得到密度为1.06～1.09g/cm 3的氯代脂肪酸酯环保增塑剂。 (3-4) Mix 5 parts by mass of refined fatty acid methyl esters and 1 part by mass of palm oil into the chlorination reaction tower, turn on the circulating pump, pass in chlorine gas, control the circulating water flow in the condenser, and maintain the reaction temperature at 85-115°C , The density reaches 1.06～1.09g/cm 3 , stop the chlorine gas and transfer the material to the degassing tower while it’s hot, bubbling in compressed air to maintain the temperature at 60～90℃, the acid value reaches 0.5mgKOH/g, stop bubbling to obtain chlorine Substitute materials; adding a composite stabilizer that accounts for 0.3wt% of the chlorinated materials to obtain a chlorinated fatty acid ester environmentally friendly plasticizer with a density of 1.06 to 1.09 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：0：0：0.05混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:0:0:0.05.
或：or:
(3-5)3质量份精制脂肪酸甲酯与1质量份棕榈油混合均匀打入氯化反应塔中，开启循环泵，通入氯气，控制冷凝器循环水流量，维持反应温度85～115℃，密度达到1.09～1.18g/cm 3，停止通氯气趁热将物料转移至脱气塔中，鼓入压缩空气维持温度60-90℃，酸值达到0.5mgKOH/g，停止鼓气，得到氯代物料；加入占氯代物料3wt％的复合稳定剂，得到密度为1.09～1.18g/cm 3的氯代脂肪酸酯环保增塑剂。 (3-5) Mix 3 parts by mass of refined fatty acid methyl esters and 1 part by mass of palm oil into the chlorination reaction tower, turn on the circulating pump, pass in chlorine gas, control the circulating water flow in the condenser, and maintain the reaction temperature at 85-115°C , The density reaches 1.09～1.18g/cm 3 , stop the chlorine gas and transfer the material to the degassing tower while it is hot, bubbling in compressed air to maintain the temperature at 60-90℃, the acid value reaches 0.5mgKOH/g, stop bubbling to obtain chlorine Substituting materials; adding a composite stabilizer accounting for 3wt% of the chlorinated materials to obtain a chlorinated fatty acid ester environmentally friendly plasticizer with a density of 1.09 to 1.18 g/cm 3.
其中，复合稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂UV531按照质量比为1：10：10：0.06混合得到。Among them, the composite stabilizer is obtained by mixing ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent UV531 in a mass ratio of 1:10:10:0.06.
对所得增塑剂的稳定性进行测试，将所得增塑剂在干燥、密封、常温条件下放置180天，测试放置前后增塑剂的色度、加热减量(在125℃下加热2h，测试加热后和加热前的质量差)、酸值、密度和热分解温度，其中实施例1中(1-1)所得增塑剂样品(记为1-1样品)的对比测试结果如表1所示：The stability of the obtained plasticizer was tested. The obtained plasticizer was placed in a dry, sealed, and room temperature condition for 180 days, and the chromaticity and heating loss of the plasticizer before and after placement were tested (heated at 125°C for 2h, test The difference in quality after heating and before heating), acid value, density and thermal decomposition temperature. The comparative test results of the plasticizer sample (recorded as 1-1 sample) obtained in (1-1) in Example 1 are shown in Table 1. Show:
表1 1-1样品的稳定性测试结果Table 1 1-1 Stability test results of samples
 To 现制1-1样品Now made 1-1 sample 放置180天后1-1样品1-1 sample after 180 days
色度(铂钴比色)Chromaticity (Platinum Cobalt Colorimetric) 2020 2020
加热减量/g(125℃，2h)Heating loss/g (125℃, 2h) 0.260.26 0.250.25
酸值/mgKOH/gAcid value/mgKOH/g 0.50.5 0.480.48
密度/g/cm 3(20℃) Density/g/cm 3 (20℃) 1.0751.075 1.0751.075
热分解温度/℃Thermal decomposition temperature/℃ 175175 174174
表1中的结果显示，所得增塑剂在干燥、密封、常温条件下保存180天，产品的性能基本没有变化。说明本发明制备的氯代脂肪酸酯环保增塑剂具有较高的质量稳定性。The results in Table 1 show that the obtained plasticizer is stored for 180 days under dry, sealed, and normal temperature conditions, and the performance of the product is basically unchanged. It shows that the environmentally friendly plasticizer of chlorinated fatty acid ester prepared by the invention has higher quality stability.
对实施例1～3中所得其他增塑剂样品进行相同的稳定性测试，测试结果显示所得增塑剂在干燥、密封、常温条件下保存180天，产品的性能均基本没有变化，说明本发明制备的增塑剂具有较高的质量稳定性。The other plasticizer samples obtained in Examples 1 to 3 were subjected to the same stability test. The test results showed that the obtained plasticizer was stored for 180 days under dry, sealed, and normal temperature conditions, and the performance of the product was basically unchanged, indicating the present invention The prepared plasticizer has high quality stability.
应用例Application example
以质量份计，取实施例1中(1-1)所得增塑剂样品、DOTP(对苯二甲酸二辛酯)各50份，分别加入100份PVC树脂粉，2份钙锌稳定剂，0.5份硬脂酸混合均匀，在双辊开炼机进行开炼，开炼好后，在平板硫化机上硫化制成PVC塑料制品；测试制品的性能，其结果如表2所示：In parts by mass, take 50 parts of each of the plasticizer sample and DOTP (dioctyl terephthalate) obtained in Example 1 (1-1), add 100 parts of PVC resin powder and 2 parts of calcium zinc stabilizer, respectively, 0.5 part of stearic acid was mixed uniformly, and then smelted in a two-roll mill. After the smelted, it was vulcanized on a flat vulcanizer to make PVC plastic products; the properties of the products were tested, and the results are shown in Table 2:
表2 1-1样品制备的PVC塑料制品性能测试结果Table 2 1-1 Performance test results of PVC plastic products prepared by samples
 To 1-1样品的制品1-1 Sample products DOTP的制品DOTP products
断裂强度(MPa)Breaking strength (MPa) 16.316.3 15.915.9
断裂伸长率(％)Elongation at break (%) 212212 209209
邵氏硬度AShore hardness A 8989 8888
表2中的结果显示，使用实施例1中(1-1)所得增塑剂加工成的PVC制品的各项物理性能与利用DOTP为增塑剂加工的制品差距不大，说明本发明制备的氯代脂肪酸酯增塑剂是一种理想的环保增塑剂。The results in Table 2 show that the physical properties of PVC products processed using the plasticizer obtained in (1-1) in Example 1 are not much different from those processed using DOTP as the plasticizer, indicating that the preparation of the present invention Chlorinated fatty acid ester plasticizer is an ideal environmentally friendly plasticizer.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The description of the above embodiments is only used to help understand the method and the core idea of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (14)

  1. 一种氯代脂肪酸酯环保增塑剂的制备方法，其特征在于，包括以下步骤：A preparation method of chlorinated fatty acid ester environmental protection plasticizer, which is characterized in that it comprises the following steps:
    (1)将棕榈油、甲醇和甲醇钠甲醇溶液混合进行酯交换反应，得到粗脂肪酸甲酯；(1) Mixing palm oil, methanol and sodium methoxide methanol solution for transesterification reaction to obtain crude fatty acid methyl ester;
    (2)将所述粗脂肪酸甲酯进行精馏，得到精制脂肪酸甲酯；(2) rectifying the crude fatty acid methyl esters to obtain refined fatty acid methyl esters;
    (3)在氯气条件下，将所述精制脂肪酸甲酯进行氯化反应，得到氯代物料；(3) Under chlorine conditions, subject the refined fatty acid methyl ester to a chlorination reaction to obtain chlorinated materials;
    (4)将所述氯代物料和稳定剂混合，得到氯代脂肪酸酯环保增塑剂。(4) Mixing the chlorinated material and the stabilizer to obtain an environmentally friendly plasticizer of chlorinated fatty acid ester.
  2. 根据权利要求1所述的制备方法，其特征在于，所述酯交换反应的温度为65～75℃，时间为0.5～1.5h。The preparation method according to claim 1, wherein the temperature of the transesterification reaction is 65-75°C, and the time is 0.5-1.5h.
  3. 根据权利要求1所述的制备方法，其特征在于，所述棕榈油的酸值≤0.6mgKOH/g，水分含量≤0.15wt％，碘值为15～38。The preparation method according to claim 1, wherein the acid value of the palm oil is ≤ 0.6 mgKOH/g, the moisture content is ≤ 0.15 wt%, and the iodine value is 15-38.
  4. 根据权利要求1所述的制备方法，其特征在于，所述甲醇钠甲醇溶液中甲醇钠的质量百分含量为27.0～31.0％；The preparation method according to claim 1, wherein the mass percentage of sodium methoxide in the sodium methoxide methanol solution is 27.0-31.0%;
  5. 根据权利要求1、3或4所述的制备方法，其特征在于，以棕榈油、甲醇和甲醇钠甲醇溶液的总质量为100％计，所述棕榈油的质量百分含量为85.0～86.4％，甲醇的质量百分含量为12.9～14.2％，甲醇钠甲醇溶液的质量百分含量为0.6～0.9％。The preparation method according to claim 1, 3 or 4, characterized in that, based on the total mass of palm oil, methanol and sodium methoxide methanol solution as 100%, the mass percentage of palm oil is 85.0-86.4% , The mass percentage of methanol is 12.9-14.2%, and the mass percentage of the sodium methoxide methanol solution is 0.6-0.9%.
  6. 根据权利要求1所述的制备方法，其特征在于，所述精馏的真空度为-0.09～-0.095Mpa，回流比为0～2，塔底温度为220～240℃，塔顶温度为170～200℃，塔板数为25～30。The preparation method according to claim 1, wherein the vacuum degree of the rectification is -0.09～-0.095Mpa, the reflux ratio is 0～2, the bottom temperature is 220～240℃, and the top temperature is 170 ～200℃, the number of plates is 25-30.
  7. 根据权利要求1所述的制备方法，其特征在于，所述氯化反应的温度为85～115℃。The preparation method according to claim 1, wherein the temperature of the chlorination reaction is 85-115°C.
  8. 根据权利要求1所述的制备方法，其特征在于，所述步骤(3)中，在氯化反应前，还包括将精制脂肪酸甲酯和棕榈油混合；所述精制脂肪酸甲酯和棕榈油的质量比为(1～9):1。The preparation method according to claim 1, characterized in that, in the step (3), before the chlorination reaction, it further comprises mixing refined fatty acid methyl esters and palm oil; the refined fatty acid methyl esters and palm oil The mass ratio is (1-9):1.
  9. 根据权利要求1所述的制备方法，其特征在于，当所述步骤(3)中不加入棕榈油时，所述氯化反应的终点的氯代物料密度为 1.06～1.25g/cm 3。 The preparation method according to claim 1, wherein when palm oil is not added in the step (3), the density of the chlorinated material at the end of the chlorination reaction is 1.06-1.25 g/cm 3 .
  10. 根据权利要求8所述的制备方法，其特征在于，当所述步骤(3)中加入棕榈油时，所述氯化反应的终点的氯代物料密度为1.06～1.18g/cm 3。 The preparation method according to claim 8, wherein when palm oil is added in the step (3), the density of the chlorinated material at the end of the chlorination reaction is 1.06-1.18 g/cm 3 .
  11. 根据权利要求1所述的制备方法，其特征在于，所述氯代物料与稳定剂混合前还包括：将所述氯代物料进行脱气，所述脱气的温度为60～90℃，脱气至氯代物料的酸值≤0.5mgKOH/g。The preparation method according to claim 1, characterized in that, before mixing the chlorinated material with the stabilizer, the method further comprises: degassing the chlorinated material, the temperature of the degassing is 60-90°C, and the degassing The acid value of gas to chlorinated materials is less than or equal to 0.5mgKOH/g.
  12. 根据权利要求1所述的制备方法，其特征在于，所述稳定剂由乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂组成，所述乙二醇缩水甘油醚、环氧脂肪酸甲酯、环氧大豆油与抗紫外剂的质量比为1:(0～20):(0～20):(0.05～0.1)。The preparation method according to claim 1, wherein the stabilizer is composed of ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil, and an anti-ultraviolet agent, and the ethylene glycol glycidyl ether The mass ratio of epoxy fatty acid methyl ester, epoxy soybean oil and anti-ultraviolet agent is 1:(0-20):(0-20):(0.05～0.1).
  13. 根据权利要求1或12所述的制备方法，其特征在于，所述稳定剂的加入量为氯代物料质量的0.3～3％。The preparation method according to claim 1 or 12, wherein the added amount of the stabilizer is 0.3-3% of the mass of the chlorinated material.
  14. 权利要求1～13任意一项所述制备方法制备的氯代脂肪酸酯环保增塑剂。An environmentally friendly plasticizer of chlorinated fatty acid ester prepared by the preparation method of any one of claims 1-13.
PCT/CN2020/109034 2020-04-20 2020-08-14 Chlorinated fatty acid ester environment-friendly plasticizer and preparation method therefor WO2021212703A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119684807A (en) * 2025-02-25 2025-03-25 潍坊迪蒙化工有限公司 Plasticizer and preparation method thereof

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111378289A (en) * 2020-04-20 2020-07-07 山东岩海建设资源有限公司 Chlorinated fatty acid ester environment-friendly plasticizer and preparation method thereof
CN111978180A (en) * 2020-07-31 2020-11-24 南京信卓化工科技有限公司 Method for tubular continuous production of chlorinated fatty acid ester
CN112592701B (en) * 2020-12-22 2022-08-09 广州江盐化工有限公司 Oil-based drilling fluid based on chlorinated fatty acid ester and preparation method and application thereof
CN113402965A (en) * 2021-08-02 2021-09-17 福建省三棵树新材料有限公司 High-bio-based-content single-component polyurethane waterproof coating and preparation method thereof
CN115181328B (en) * 2022-07-21 2024-04-02 浙江嘉澳环保科技股份有限公司 Preparation method of chloroepoxy fatty acid methyl ester compound or primary plasticizer and product
CN116082947B (en) * 2022-12-06 2023-09-29 石家庄东翔化工有限公司 Low-viscosity polyurethane quick-drying spray coating and preparation method and application thereof
CN116283891B (en) * 2023-04-07 2024-09-10 广东鑫达新材料科技有限公司 Flexible high-molecular modified epoxidized soybean oil high-molecular plasticizer, and preparation method and application thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2969339A (en) * 1956-07-02 1961-01-24 Dehydag Gmbh Chlorinated triglycerides of fatty acids as secondary plasticizers for polyvinyl chloride
JPS4533294B1 (en) * 1962-03-02 1970-10-26
CN101704962A (en) * 2009-11-13 2010-05-12 广州大学 Method for preparing chlorinated alkoxy biomass plasticizer
CN103193637A (en) * 2013-04-01 2013-07-10 福建致尚生物质材料发展有限公司 Preparation method of bio-ester plasticizing agent
CN108849871A (en) * 2018-08-22 2018-11-23 苏州丰倍生物科技有限公司 Environment-friendly oil phase for dispersible oil suspending agent containing mesosulfuron-methyl and preparation method thereof
CN109651826A (en) * 2018-12-19 2019-04-19 嘉兴若天新材料科技有限公司 A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer
CN109971551A (en) * 2019-03-28 2019-07-05 福建省明洲环保发展有限公司 A kind of method and product preparing environmentally friendly chloro plasticizer by waste grease
CN110317135A (en) * 2019-07-08 2019-10-11 河北金谷再生资源开发有限公司 Utilize production of biodiesel chlorinated fatty acid methyl esters technique
CN110922634A (en) * 2019-11-05 2020-03-27 石家庄东翔化工有限公司 High-viscosity environment-friendly plasticizer and preparation method and application thereof
CN111151199A (en) * 2020-02-12 2020-05-15 浙江镇洋发展股份有限公司 Continuous production device and process of chlorinated fatty acid methyl ester
CN111378289A (en) * 2020-04-20 2020-07-07 山东岩海建设资源有限公司 Chlorinated fatty acid ester environment-friendly plasticizer and preparation method thereof
CN111517951A (en) * 2020-05-15 2020-08-11 福建致尚生物质材料发展有限公司 Method for preparing methyl chloropalmitate plasticizer by using palmitic acid

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2969339A (en) * 1956-07-02 1961-01-24 Dehydag Gmbh Chlorinated triglycerides of fatty acids as secondary plasticizers for polyvinyl chloride
JPS4533294B1 (en) * 1962-03-02 1970-10-26
CN101704962A (en) * 2009-11-13 2010-05-12 广州大学 Method for preparing chlorinated alkoxy biomass plasticizer
CN103193637A (en) * 2013-04-01 2013-07-10 福建致尚生物质材料发展有限公司 Preparation method of bio-ester plasticizing agent
CN108849871A (en) * 2018-08-22 2018-11-23 苏州丰倍生物科技有限公司 Environment-friendly oil phase for dispersible oil suspending agent containing mesosulfuron-methyl and preparation method thereof
CN109651826A (en) * 2018-12-19 2019-04-19 嘉兴若天新材料科技有限公司 A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer
CN109971551A (en) * 2019-03-28 2019-07-05 福建省明洲环保发展有限公司 A kind of method and product preparing environmentally friendly chloro plasticizer by waste grease
CN110317135A (en) * 2019-07-08 2019-10-11 河北金谷再生资源开发有限公司 Utilize production of biodiesel chlorinated fatty acid methyl esters technique
CN110922634A (en) * 2019-11-05 2020-03-27 石家庄东翔化工有限公司 High-viscosity environment-friendly plasticizer and preparation method and application thereof
CN111151199A (en) * 2020-02-12 2020-05-15 浙江镇洋发展股份有限公司 Continuous production device and process of chlorinated fatty acid methyl ester
CN111378289A (en) * 2020-04-20 2020-07-07 山东岩海建设资源有限公司 Chlorinated fatty acid ester environment-friendly plasticizer and preparation method thereof
CN111517951A (en) * 2020-05-15 2020-08-11 福建致尚生物质材料发展有限公司 Method for preparing methyl chloropalmitate plasticizer by using palmitic acid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119684807A (en) * 2025-02-25 2025-03-25 潍坊迪蒙化工有限公司 Plasticizer and preparation method thereof

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