CN112940424A - Flame-retardant degradable plastic and preparation method thereof - Google Patents
Flame-retardant degradable plastic and preparation method thereof Download PDFInfo
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- C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
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Abstract
The invention relates to a degradable plasticAnd a preparation method thereof, the degradable plastic comprises the following components: 45-70 parts of modified polyvinyl alcohol, 30-60 parts of starch, 3-8 parts of glycerol, 10-23 parts of hydroxypropyl cellulose and modified SiO217-34 parts of nano particles and 0.3-0.8 part of antioxidant; the modified polyvinyl alcohol is flame retardant modified polyvinyl alcohol, and the flame retardant is 2-hydroxy-5, 5-dimethyl-2, 2-oxo-1, 3, 2-dioxaphosphorite ethanolamine salt (PNOEA). The invention has the beneficial effects that (1) the polyvinyl alcohol is modified by adopting the novel flame retardant, and the prepared modified polyvinyl alcohol resin has better flame retardant effect and better mechanical property; (2) by using modified SiO2The nano particles are used as the filler, so that the dispersion performance of the degradable plastic is improved, and the prepared degradable plastic has better mechanical property.
Description
Technical Field
The invention belongs to the technical field of degradable plastics, and particularly relates to a flame-retardant degradable plastic and a preparation method thereof.
Background
The plastic packaging bag is a packaging bag which takes plastic as a raw material and is used for producing various articles in daily life, and is widely used in daily life and industrial production. The plastic packaging bag provides convenience for consumers, and causes serious energy resource waste and environmental pollution due to excessive use, incomplete recycling and the like. Especially, the ultrathin plastic shopping bags are easy to be damaged and mostly discarded at will, and become the main source of white pollution. More and more countries and regions have limited the production, sale and use of plastic shopping bags. Based on the purpose, degradable plastics are available on the market, and the degradable plastics refer to plastics which have various properties meeting the use requirements, have unchanged performance in the preservation period, can be degraded into environmentally-friendly substances in the natural environment after being used, are different from three major synthetic plastics and are mainly prepared from plant straws and the like. The currently developed degradable plastics include photodegradable plastics, photobiodegradable plastics, photooxidized biodegradable plastics, high starch content type biodegradation, high calcium carbonate filling type photooxidative degradation, full biodegradation and the like. For example, patent technology CN111607131A discloses a master batch of degradable plastics and a preparation method thereof, which comprises the following raw materials by mass: 20-40% of polyvinyl alcohol, 50-70% of natural starch, 2-6% of plasticizer, 1-4% of modified attapulgite and the like; CN110713624A discloses a starch-based cellulose degradable plastic film, which mainly comprises polyvinyl alcohol, corn starch, hydroxypropyl cellulose, modified silica sol, glycerol and other components. It is not easy to find that the existing products contain flammable substances such as polyvinyl alcohol, starch and the like, particularly polyvinyl alcohol, the limiting oxygen index of the polyvinyl alcohol is lower than 20%, and the use of the polyvinyl alcohol-based degradable plastic is seriously influenced.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a flame-retardant degradable plastic and a preparation method thereof, and the specific scheme is as follows:
a flame retardant degradable plastic, the components of which comprise: 45-70 parts of modified polyvinyl alcohol, 30-60 parts of starch, 3-8 parts of glycerol, 10-23 parts of hydroxypropyl cellulose and modified SiO217-34 parts of nano particles and 0.3-0.8 part of antioxidant;
the modified polyvinyl alcohol is flame retardant modified polyvinyl alcohol, and the flame retardant is 2-hydroxy-5, 5-dimethyl-2, 2-oxo-1, 3, 2-dioxaphosphorite ethanolamine salt (PNOEA);
the PNOEA structure is as follows:
the preparation route of the flame retardant is as follows:
the preparation process comprises the following steps: dimethyl propylene glycol and phosphorus oxychloride react in chloroform to obtain phosphorus oxychloride, and the phosphorus oxychloride is hydrolyzed to obtain hydroxyl phosphate, and finally the hydroxyl phosphate reacts with ethanolamine to obtain a flame retardant product.
Furthermore, the PNOEA can be combined with ammonium polyphosphate (APP) for use, the flame retardant effect after combination is better, and the optimal ratio of the PNOEA to the APP is 3-4: 1.
The modification steps of the polyvinyl alcohol are as follows: fully mixing the composite flame retardant and polyvinyl alcohol according to a mass ratio, and then adding a proper amount of metal chelating agent for full mixing to prepare modified polyvinyl alcohol; the metal chelating agent is CuSAO (salicylaldoxime copper metal chelating agent); the SAO in the metal chelating agent inhibits the generation of alkoxy oxygen free radicals at high temperature and simultaneously generates stable phenoxy oxygen free radicals. During the combustion process, the metal chelating agent is destroyed to generate free metal ions, further increasing the oxygen index.
Because the traditional ammonium polyphosphate flame retardant and polyvinyl alcohol are subjected to eutectic modification by physical modification, the intermolecular acting force between the flame retardant and the polyvinyl alcohol is weak, and when the addition amount of the flame retardant is too large, the toughness of the modified polyvinyl alcohol is reduced, and the mechanical property is reduced. According to the invention, PNOEA is used as a flame retardant, ethanolamine cations are introduced under the condition of maintaining a phosphate flame-retardant structure, hydroxyl in the cations can interact with polyvinyl alcohol for graft modification, and anions with a phosphate structure are inserted into a network structure of the polyvinyl alcohol, so that gaps among networks are increased, and a toughening effect is achieved.
The starch is natural starch, and comprises at least one of sweet potato starch, tapioca starch, corn starch or wheat starch.
The modified nano silicon dioxide particles are bis- [ gamma- (triethoxysilyl) propyl]Tetrasulfide (Si69) to SiO2Chemically modifying the nano particles; modified SiO2The dispersibility of the nano particles is greatly improved, the interface effect with plastics such as polyvinyl alcohol and the like is reduced, and the mechanical property is better.
The antioxidant is hindered phenol antioxidant, and comprises at least one of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The preparation method of the flame-retardant degradable plastic specifically comprises the following steps:
(1) modification of polyvinyl alcohol: and fully mixing the flame retardant and the polyvinyl alcohol according to the mass ratio, and adding a proper amount of metal chelating agent to prepare the modified polyvinyl alcohol.
(2)SiO2Modifying the nano particles: firstly, SiO is firstly2Dispersing the nano particles in ethanol to obtain a dispersion liquid; then bis- [ gamma- (triethoxysilyl) propyl group]Fully mixing tetrasulfide, ethanol and water, and then performing ultrasonic dispersion to prepare a mixed solution; finally, adding the mixed solution into the dispersion liquid for reaction, and filtering, washing and drying the mixture after the reaction is finished to obtain the modified SiO2Nanoparticles.
(3) Weighing modified polyvinyl alcohol, starch and hydroxypropyl cellulose according to a weight ratio, and adding the weighed materials into a grinder for grinding to obtain a powder mixture; mixing the prepared powder mixture with glycerol, modified SiO2 nanoparticles and an antioxidant according to a weight ratio, adding the mixture into a high-temperature reaction kettle for melt mixing, and then carrying out extrusion molding on the melt mixture to obtain the master batch.
The invention has the beneficial effects that (1) the polyvinyl alcohol is modified by adopting the novel flame retardant, and the prepared modified polyvinyl alcohol resin has better flame retardant effect and better mechanical property; (2) by using modified SiO2The nano particles are used as the filler, so that the dispersion performance of the degradable plastic is improved, and the prepared degradable plastic has better mechanical property.
Detailed Description
The present invention is further described below with reference to examples, which are only some examples of the present invention. Based on the embodiments of the present invention, those skilled in the art can make equivalent substitutions or improvements without making creative efforts and are within the protection scope of the present invention.
Preparation of flame retardant
The preparation method of the flame retardant 2-hydroxy-5, 5-dimethyl-2, 2-oxo-1, 3, 2-dioxaphosphorin alkaloid ethanolamine salt (PNOEA) comprises the following steps:
the detailed preparation example is as follows:
(1) adding dimethyl propylene glycol (1040g, 10mol) and 3000mL of trichloromethane into a reaction kettle, violently stirring at 50 ℃, dropwise adding phosphorus oxychloride, heating to 60 ℃ after dropwise adding, keeping the temperature for reaction for 6 hours, and distilling off the trichloromethane to obtain an acyl chloride white solid after the reaction is finished;
(2) dissolving the acyl chloride prepared in the step two into water, carrying out reflux reaction for 2 hours until hydrolysis is finished, and then cooling to room temperature;
(3) and (3) adding ethanolamine (610.8g,10mol) dropwise into the reaction solution prepared in the step (2), controlling the temperature in the dropwise adding process to be 5-10 ℃, reacting at room temperature for half an hour after the dropwise adding is finished, and distilling off excessive water after the reaction is finished to obtain waxy white solid, namely 2-hydroxy-5, 5-dimethyl-2, 2-oxo-1, 3, 2-dioxaphosphorine ethanolamine salt (PNOEA).
Preparation of modified silicon dioxide nano particles
For increasing SiO2The dispersing property of nano particles is characterized by that said invention adopts silane coupling agent bis- [ gamma- (triethoxysilyl) propyl group]The tetrasulfide modifies the same, and the specific process is as follows:
(1) 2kg of SiO2Dispersing the nano particles in 40L of ethanol at normal temperature, and stirring for 3h for later use;
(2) fully mixing 4kg of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, 20L of ethanol and 40mL of water, and then carrying out ultrasonic dispersion to prepare a mixed solution;
(3) adding the mixed solution prepared in the step (2) into the dispersion prepared in the step (1), stirring for 3 hours at a constant temperature of 60 ℃, filtering, washing and drying to obtain modified SiO2Nanoparticles.
Preparation of degradable plastics
Example 1
The embodiment provides a flame-retardant degradable plastic, and the components of the degradable plastic comprise: 50 parts of modified polyvinyl alcohol, 33 parts of corn starch, 6 parts of glycerol, 10 parts of hydroxypropyl cellulose and modified SiO220 parts of nano particles and 0.3 part of 2, 6-tertiary butyl-4-methylphenol; the modified polyvinyl alcohol is jointly modified by PNOEA and CuSAO;
the preparation method of the flame-retardant degradable plastic comprises the following specific steps:
(1) modification of polyvinyl alcohol: fully mixing 230g of PNOEA and 500g of polyvinyl alcohol according to a mass ratio, adding the mixture into 2000mL of ethanol, fully stirring the mixture until the mixture is completely dissolved, adding 2.3g of CuSAO, performing ultrasonic dispersion, and performing reduced pressure distillation to remove ethanol to obtain modified polyvinyl alcohol;
(2)SiO2modifying the nano particles: 500g of SiO are first introduced2Dispersing the nano particles in 1000mL of ethanol to obtain a dispersion liquid; then 15g of bis- [ gamma- (triethoxysilyl) propyl ] are added]Fully mixing tetrasulfide, 45mL of ethanol and 5mL of water, and performing ultrasonic dispersion to prepare a mixed solution; finally, adding the mixed solution into the dispersion liquid for reaction, and reacting after the reaction is finishedFiltering, washing and drying to obtain modified SiO2Nanoparticles.
(3) Weighing 500g of modified polyvinyl alcohol, 330g of corn starch and 100g of hydroxypropyl cellulose according to the weight ratio, and adding the weighed materials into a pulverizer to pulverize to obtain a powder mixture; mixing the prepared powder mixture with 180g of glycerol, 200g of modified SiO2 nanoparticles and 3g of 2, 6-tertiary butyl-4-methylphenol according to the weight ratio, adding the mixture into a high-temperature reaction kettle for melt mixing, and then carrying out extrusion molding on the melt mixture to obtain the master batch.
Example 2
The embodiment provides a flame-retardant degradable plastic, and the components of the degradable plastic comprise: 55 parts of modified polyvinyl alcohol, 43 parts of sweet potato starch, 5 parts of glycerol, 20 parts of hydroxypropyl cellulose and modified SiO230 parts of nano particles and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid]0.3 part of pentaerythritol ester; the modified polyvinyl alcohol is jointly modified by PNOEA and CuSAO;
the preparation method of the flame-retardant degradable plastic disclosed by the embodiment is the same as that of the embodiment 1, and only equivalent replacement of all components is needed.
Example 3
The embodiment provides a flame-retardant degradable plastic, and the components of the degradable plastic comprise: 55 parts of modified polyvinyl alcohol, 50 parts of corn starch, 8 parts of glycerol, 20 parts of hydroxypropyl cellulose and modified SiO228 parts of nano particles and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid]0.3 part of pentaerythritol ester; the modified polyvinyl alcohol is jointly modified by PNOEA, APP and CuSAO;
the preparation method of the flame-retardant degradable plastic comprises the following modification steps of: fully mixing 180g of PNOEA, 50g of APP and 500g of polyvinyl alcohol according to a mass ratio, adding 2000mL of ethanol and 100mL of water, fully stirring until the mixture is completely dissolved, adding 3.1g of CuSAO, performing ultrasonic dispersion, and performing reduced pressure distillation to remove ethanol to obtain modified polyvinyl alcohol;
the second and third steps of the preparation process are the same as example 1.
Example 4
The embodiment provides a flame-retardant degradable plasticThe degradable plastic comprises the following components: 68 parts of modified polyvinyl alcohol, 50 parts of wheat starch, 8 parts of glycerol, 18 parts of hydroxypropyl cellulose and modified SiO234 parts of nano particles and 0.7 part of bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether; the modified polyvinyl alcohol is jointly modified by PNOEA, APP and CuSAO;
the preparation method of the flame-retardant degradable plastic is the same as that of the embodiment 3, and only the components are replaced by the same amount.
Comparative example:
the comparative example provides degradable plastic prepared by the prior art, which comprises 35 parts of polyvinyl alcohol, 64 parts of corn starch, 5 parts of urea plasticizer and 28 parts of nano silicon dioxide. The preparation process comprises the steps of fully mixing the components according to the mass ratio, and carrying out melt extrusion molding to obtain the master batch.
The degradable plastics prepared in the above examples and comparative examples were respectively subjected to the test of mechanical properties and flame retardancy (Table 1), in which
And (3) testing mechanical properties: the procedure is carried out in accordance with GB1040-2006 in a materials testing machine. The stretching speed is 50 mm/min;
flame retardant rating: the flame retardant rating is tested by adopting UL-94 standard;
testing of flame retardant Properties: GB/T10707-2008 combustion performance measurement oxygen index method.
TABLE 1 mechanical property and water absorption of degradable plastic film
As can be seen from the data in Table 1, the flame retardant property of the degradable plastic prepared by the invention is obviously improved, and the degradable plastic has better mechanical property. The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. Flame-retardant degradable plastic and component package thereofComprises the following steps: 45-70 parts of modified polyvinyl alcohol, 30-60 parts of starch, 3-8 parts of glycerol, 10-23 parts of hydroxypropyl cellulose and modified SiO217-34 parts of nano particles and 0.3-0.8 part of antioxidant; the modified polyvinyl alcohol is flame retardant modified polyvinyl alcohol, and the flame retardant is 2-hydroxy-5, 5-dimethyl-2, 2-oxo-1, 3, 2-dioxaphosphorite ethanolamine salt (PNOEA).
2. The flame-retardant degradable plastic according to claim 1, wherein the PNOEA has the following structure:
the preparation route of the flame retardant is as follows:
the preparation process comprises the following steps: dimethyl propylene glycol and phosphorus oxychloride react in chloroform to obtain phosphorus oxychloride, and the phosphorus oxychloride is hydrolyzed to obtain hydroxyl phosphate, and finally the hydroxyl phosphate reacts with ethanolamine to obtain a flame retardant product.
3. The flame-retardant degradable plastic as claimed in claim 1, wherein the PNOEA can be used in combination with ammonium polyphosphate (APP), the flame-retardant effect is better after the combination, and the optimal ratio of PNOEA to APP is 3-4: 1.
4. The flame-retardant degradable plastic according to claim 1, wherein the polyvinyl alcohol is modified by the following steps: fully mixing the composite flame retardant and polyvinyl alcohol according to a mass ratio, and then adding a proper amount of metal chelating agent for full mixing to prepare modified polyvinyl alcohol; the metal chelator is CuSAO (salicylaldoxime copper metal chelator).
5. The flame retardant and degradable plastic according to claim 1, wherein the starch is natural starch comprising at least one of sweet potato starch, tapioca starch, corn starch or wheat starch.
6. The flame-retardant degradable plastic according to claim 1, wherein the modified nano-silica particles are bis- [ gamma- (triethoxysilyl) propyl ] group]Tetrasulfide (Si69) to SiO2The nanoparticles are chemically modified.
7. The flame retardant degradable plastic according to claim 1, wherein the antioxidant is a hindered phenol antioxidant comprising at least one of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide, and pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ].
8. The preparation method of the flame-retardant degradable plastic disclosed by any one of claims 1-7, which specifically comprises the following steps:
(1) modification of polyvinyl alcohol: fully mixing a flame retardant and polyvinyl alcohol according to a mass ratio, and adding a proper amount of metal chelating agent to prepare modified polyvinyl alcohol;
(2)SiO2modifying the nano particles: firstly, SiO is firstly2Dispersing the nano particles in ethanol to obtain a dispersion liquid; then bis- [ gamma- (triethoxysilyl) propyl group]Fully mixing tetrasulfide, ethanol and water, and then performing ultrasonic dispersion to prepare a mixed solution; finally, adding the mixed solution into the dispersion liquid for reaction, and filtering, washing and drying the mixture after the reaction is finished to obtain the modified SiO2Nanoparticles;
(3) weighing modified polyvinyl alcohol, starch and hydroxypropyl cellulose according to a weight ratio, and adding the weighed materials into a grinder for grinding to obtain a powder mixture; mixing the prepared powder mixture with glycerol, modified SiO2 nanoparticles and an antioxidant according to a weight ratio, adding the mixture into a high-temperature reaction kettle for melt mixing, and then carrying out extrusion molding on the melt mixture to obtain the master batch.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120543A (en) * | 2022-09-09 | 2023-05-16 | 江苏江山红化纤有限责任公司 | Preparation method of flame-retardant graphene polyamide 6 composite material |
| CN119060417A (en) * | 2024-11-07 | 2024-12-03 | 台州黄岩泽钰新材料科技有限公司 | A starch-based degradable composite material and preparation method thereof |
-
2021
- 2021-01-28 CN CN202110117871.1A patent/CN112940424A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120543A (en) * | 2022-09-09 | 2023-05-16 | 江苏江山红化纤有限责任公司 | Preparation method of flame-retardant graphene polyamide 6 composite material |
| CN119060417A (en) * | 2024-11-07 | 2024-12-03 | 台州黄岩泽钰新材料科技有限公司 | A starch-based degradable composite material and preparation method thereof |
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