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CN112480169A - Liquid phosphorus-containing compound and application and preparation method thereof - Google Patents

Liquid phosphorus-containing compound and application and preparation method thereof Download PDF

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Publication number
CN112480169A
CN112480169A CN202011440568.7A CN202011440568A CN112480169A CN 112480169 A CN112480169 A CN 112480169A CN 202011440568 A CN202011440568 A CN 202011440568A CN 112480169 A CN112480169 A CN 112480169A
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formula
compound
containing compound
phosphorus
alkyl
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卓其聪
王林冲
谢颖仪
杨德兵
农林
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NANXIONG ZHIYI FINE CHEMICAL CO Ltd
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NANXIONG ZHIYI FINE CHEMICAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4866—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the ester moiety containing a substituent or structure which is considered as characteristic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4866—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the ester moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4875—Esters with hydroxy aryl 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5377—Phosphinous compounds, e.g. R2=P—OR'
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

The invention discloses a liquid phosphorus-containing compound, which has a structure shown in a formula 1, wherein the formula 1 is as follows:
Figure DDA0002821917880000011
wherein R is1、R2、R3Each independently selected from phenyl or-O-R4，R4Is C8-C15 alkyl or a group of formula 2, formula 2:
Figure DDA0002821917880000012
wherein R is5Is C10-C18 alkyl or alkenyl. The compound has the advantages of simple preparation process, low cost, high purity and yield of the prepared phosphorus-containing compound, excellent performance, good stability, excellent hydrolysis resistance and excellent aging resistance; meanwhile, the phosphorus-containing compound prepared by the method is used as an additive to prepare a high polymer material, so that the aging resistance of the material can be effectively improved, and the phosphorus-containing compound has the characteristics of convenience in addition and good dispersibility when being used in a liquid polymer material.

Description

Liquid phosphorus-containing compound and application and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials and additives, in particular to a liquid phosphorus-containing compound and an application and a preparation method thereof.
Background
The polymer material is also called polymer material, and is a material composed of a polymer compound as a matrix and other additives (auxiliaries). The polymer material is the fourth largest material following steel, cement and wood. The high polymer material has the advantages of rich raw material sources, simple and convenient processing and forming, low production cost, low manufacturing energy consumption, light weight and the like, and generally has good mechanical, electrical and optical properties. Plastics, synthetic fibers and synthetic rubbers and are referred to as polymeric three-major synthetic materials. Although polymer materials have been rapidly developed because of the advantages that many metals and inorganic materials cannot be substituted for them, polymer materials which are used only under ordinary conditions, so-called general-purpose polymers, have been produced on a large scale. Because of their reactive properties with oxygen, they are degraded during storage and use when they are affected by light, high temperature, heavy metal ions, mechanical shear, etc., thereby affecting the stability of the polymer material during processing and long-term thermal stability, and their physical and mechanical properties and appearance are also impaired, so that the product value and use value are lost.
With the continuous improvement of the living standard of people and the continuous development of modern engineering technology, the safety, sanitation and environmental protection of the high polymer material are in line with the requirements of higher updating. Therefore, research and development of various additives in polymer materials are receiving more and more attention and attention from various research institutions and researchers, and various additives in polymer materials are also the focus of research at present. Not only the influence on the product performance needs to be considered, but also the factors such as environmental protection, cost and the like are all the problems which need to be considered and solved at present. The antioxidant TNPP is a phosphite antioxidant, although the performance of the antioxidant is excellent, the harm of nonyl phenol used in the preparation raw material to the environment and human bodies is great, so that the wide application of the TNPP is limited; in addition, phosphite antioxidants generally have the problem of not being resistant to hydrolysis.
A bis (2, 4-di-tert-butylphenol) phenylphosphonite compound and a synthesis method thereof are reported in a patent with the patent number of 201210474011.4, a synthesis method of diphenylphosphine cumylphenol ester is also reported in a patent with the patent application number of 201410269635.1, phosphonites containing phosphorus-carbon bonds have excellent heat resistance and hydrolysis resistance, but phosphorus-carbon bond compounds synthesized by raw materials such as 2, 4-di-tert-butylphenol and cumylphenol are mostly solid products, and the phosphorus-carbon bond compounds are not uniformly dispersed in liquid polymer materials such as polyurethane, epoxy resin and rubber emulsion and are inconvenient to use, and the application of the phosphorus-carbon bond compounds in the liquid polymer materials is limited by the problems.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a liquid phosphorus-containing compound having a structure represented by formula 1, formula 1:
Figure BDA0002821917870000021
wherein R is1、R2、R3Each independently selected from phenyl or-O-R4，R4Is C8-C15 alkyl or a group of formula 2, formula 2:
Figure BDA0002821917870000022
wherein R is5Is C10-C18 alkyl or alkenyl; the liquid phosphorus-containing compound is a flowable liquid at room temperature.
As a preferable technical scheme, the alkyl of C8-C15 is a straight-chain alkyl of C8-C15 or a branched-chain alkyl of C8-C15.
As a preferable technical scheme, the alkyl or alkenyl of C10-C18 is a linear chain or branched chain structure of C10-C18.
As a preferred technical scheme, the R is1、R2、R3At least one of which is-O-R4。
As a preferred technical scheme, the raw material for preparing the phosphorus-containing compound comprises a compound a shown as a formula 3, wherein the formula 3:
Figure BDA0002821917870000023
wherein R is6、R7、R8Each independently selected from a halogen atom or a phenyl group;
the preparation raw materials also comprise a compound B shown as a formula 4, and the formula 4 is as follows:
Figure BDA0002821917870000024
wherein R is9Is C10-C18 alkyl or alkenyl.
As another preferred embodiment, the compound B is replaced with a compound C represented by formula 5, formula 5: r10-OH, wherein R10Is C8-C15 alkyl.
As a preferred technical scheme, the R is6、R7、R8At least one of which is a halogen atom.
A second aspect of the invention provides the use of a phosphorus-containing compound as described above in a polymeric material.
A third aspect of the present invention provides a process for the preparation of a phosphorus-containing compound as described above, comprising the steps of: and (3) the molar ratio of the halogen atoms to the phenolic hydroxyl groups of the compound A to the compound B is 1: (1-1.5) carrying out the reaction.
As another preferred technical solution, the preparation method comprises the following steps: the molar ratio of the halogen atoms to the alcoholic hydroxyl groups of the compound A to the compound C is 1: (1-1.5) carrying out the reaction.
Has the advantages that: the invention provides a phosphorus-containing compound which is used as a polymer additive, the preparation process is simple, the cost is lower, the purity and the yield of the prepared phosphorus-containing compound are higher, the performance is excellent, the stability is better, and the hydrolysis resistance and the aging resistance are excellent; meanwhile, the phosphorus-containing compound prepared by the method is used as an additive to prepare a high polymer material, so that the aging resistance of the material can be effectively improved.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
In order to solve the above problems, a first aspect of the present invention provides a phosphorus-containing compound having a structure represented by formula 1, formula 1:
Figure BDA0002821917870000041
wherein R is1、R2、R3Each independently selected from phenyl or-O-R4，R4Is C8-C15 alkyl or a group of formula 2, formula 2:
Figure BDA0002821917870000042
wherein R is5Is C10-C18 alkyl or alkenyl; the liquid phosphorus-containing compound is a flowable liquid at room temperature.
In some preferred embodiments, R is1、R2、R3At least one of which is-O-R4。
In some preferred embodiments, the C8-C15 alkyl is C8-C15 straight chain alkyl or C8-C15 branched chain alkyl; further preferably, the alkyl of C8-C15 is a branched alkyl of C8-C15.
In some preferred embodiments, the C10-C18 alkyl or alkenyl group is a C10-C18 linear or branched structure; more preferably, the alkyl or alkenyl group of C10-C18 is a linear structure of C10-C18.
The inventor finds that the space configuration of the three-coordinate phosphorus compound is sp3 hybridized triangular cone, phosphorus atoms carry lone pair electrons, a strong P ═ O bond can be formed during reaction, the bond energy is up to 611kJ/mol, so peroxide generated in the oxidation process can be decomposed to form a stable inactive product, the oxidation process of a high polymer material is delayed, and the service life of the product is prolonged, however, phosphorus elements have nucleophilic action and large volume, are easy to be attacked by water molecules, and then are hydrolyzed, so that the antioxidation effect is ineffective. The inventor finds that the hydrolysis resistance of the compound can be obviously improved by introducing a group with larger steric hindrance around a phosphorus atom, but the reaction of the corresponding phosphorus element and peroxide is also inhibited to a certain extent, so that the conditions of steric hindrance, electronegativity and the like around the phosphorus atom in the phosphorus-containing compound need to be controlled, so that the hydrolysis resistance and the oxidation resistance of the phosphorus-containing compound are balanced.
When R is considered to improve the hydrolysis resistance of the phosphorus-containing compound4When C8-C15 alkyl is used, in some preferred embodiments, the C8-C15 alkyl is C8-C15 branched alkyl; when R is considered to balance the hydrolysis resistance and the oxidation resistance of the phosphorus-containing compound4When it is a group represented by the formula 2, R5Is C12-C15 alkyl.
In some preferred embodimentsIn an embodiment, the raw material for preparing the phosphorus-containing compound includes a compound a shown in formula 3, formula 3:
Figure BDA0002821917870000051
wherein R is6、R7、R8Each independently selected from a halogen atom or a phenyl group;
the preparation raw materials also comprise a compound B shown as a formula 4, and the formula 4 is as follows:
Figure BDA0002821917870000052
wherein R is9Is C10-C18 alkyl or alkenyl.
In some preferred embodiments, R is6、R7、R8At least one of which is a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; preferably a chlorine atom.
In some preferred embodiments, R is9Is a branched alkyl group of C12-C15.
In other preferred embodiments, compound B is replaced with compound C according to formula 5, formula 5: r10-OH, wherein R10Is C8-C15 alkyl; further preferably, R is10A branched alkyl group of C8-C15; further, said R10Is a branched alkyl group of C8-C12.
As examples of the compound A, phosphorus trichloride (CAS No. 7719-12-2), diphenyl phosphine monochloride (CAS No. 1079-66-9), phenyl phosphine dichloride (CAS No. 644-97-3) can be exemplified.
In some preferred embodiments, R is6、R7、R8Each independently selected from a halogen atom or a phenyl group; the phenyl is alkyl substituted phenyl. In this embodiment, as examples of the compound A, di (tolyl) monochlorophosphine (CAS number: 1019-71-2), di (ethylphenyl) monochlorophosphine, tolyldichlorophosphine, ethylphenyldichlorophosphine, and the like can be illustrated.
As examples of the compound B, dodecylphenol (CAS number: 27193-86-8, a mixture of ortho-dodecylphenol and para-dodecylphenol), cardanol (CAS number: 501-24-6) can be exemplified.
As examples of the compound C, isooctanol (CAS number: 104-76-7), 3-ethyl-2-heptanol (CAS number: 19780-39-3), 2, 4-diethyl-1-heptanol (CAS number: 80192-55-8), 5-ethyl-3-nonanol (CAS number: 19780-71-3) can be exemplified.
The second aspect of the present invention provides a method for producing a phosphorus-containing compound as described above, which comprises the following steps when the raw materials for producing the phosphorus-containing compound are compound a and compound B: and (3) the molar ratio of the halogen atoms to the phenolic hydroxyl groups of the compound A to the compound B is 1: (1-1.5) carrying out the reaction.
In some preferred embodiments, when the starting materials for the preparation of the phosphorus-containing compound are compound a and compound C, the preparation process comprises the steps of: the molar ratio of the halogen atoms to the alcoholic hydroxyl groups of the compound A to the compound C is 1: (1-1.5) carrying out the reaction.
When compound a is reacted with compound B, in some preferred embodiments, the preparation method comprises the steps of: taking compound B, passing through N2And (3) replacing, namely dripping the compound A at the temperature of 60-150 ℃, heating to 150-210 ℃ after dripping, carrying out heat preservation reaction until no obvious hydrogen chloride gas is generated, vacuumizing, decompressing and distilling to remove the solvent and the excessive compound B, and cooling to obtain the product.
When compound a is reacted with compound B, in other preferred embodiments, the preparation method comprises the steps of: adding the compound B and a solvent into a reaction container in sequence, mixing the compound A and the solvent at a certain temperature, dropwise adding into the reaction container, continuously reacting for 2-4 h after dropwise adding at 80-150 ℃, heating to 150-180 ℃, keeping the temperature at 150-180 ℃ for reacting for 2-6 h, continuously heating to 200-220 ℃, receiving the evaporated solvent during heating, and performing vacuum-pumping and pressure-reducing evaporation to remove residual solvent and excessive compound B to obtain the product.
When compound a is reacted with compound C, in some preferred embodiments, the preparation method comprises the steps of: adding the compound C, a catalyst and a solvent into a reaction vessel in sequence, mixing the compound A and the solvent at a certain temperature, dropwise adding into the reaction vessel, continuously reacting for 2-4 h after dropwise adding at-10-30 ℃, heating to 150-180 ℃, receiving the evaporated catalyst and solvent, reacting for 1-3 h at 150-180 ℃, evaporating residual catalyst, solvent and excessive compound C under reduced pressure, cooling, filtering, washing the filtrate with a sodium carbonate aqueous solution, separating liquid, performing vacuum dehydration on an oil phase, and adding diatomite for circular filtration to obtain the product.
The inventor finds that R in the compound A in the development process6、R7、R8When one or two of the halogen atoms are halogen atoms, one or two alkoxy or phenoxy groups are correspondingly introduced into the phosphorus-containing compound obtained by the reaction, compared with R in the compound A6、R7、R8The hydrolysis resistance of the product prepared by adopting halogen atoms is further improved because the P-C bond in the P-Ph (benzene ring) is more stable than the P-O-C bond in the P-O-R (R is alkyl or phenyl), the steric hindrance around the phosphorus atom is larger, the interaction between water molecules and the phosphorus atom is not facilitated, and the stability of the phosphorus-containing compound is improved.
In some preferred embodiments, the solvent has a boiling range of 100 to 300 ℃; more preferably, the boiling range of the solvent is 140-200 ℃. As an example of the solvent, the solvent can be selected from No. 6 solvent oil, No. 120 solvent oil and No. 200 solvent oil, and 120# or 200# solvent oil is preferred. The inventor finds that when the solvent has a proper boiling range, hydrogen chloride gas can be effectively taken out, and the production cost is reduced. In the invention, the addition of solvents such as 120# solvent oil and 200# solvent oil for reaction is unexpectedly found, so that the color of a final product can be obviously reduced, and analysis shows that on one hand, the addition of the solvents can effectively take away hydrogen chloride gas, and the occurrence of side reactions in which the hydrogen chloride participates is reduced; on the other hand, the hydrogen chloride gas added into the solvent is easier to be evaporated out, so that the introduction of iron ions is reduced in the processes of reducing the residual chlorine in the reaction system and contacting a stainless steel pipeline in the later stage.
The boiling range in the present application means that the temperature at which the first drop of liquid begins to drop in the condenser tube is the initial distillation temperature, the temperature at which distillation is nearly completed is the final distillation temperature, and the interval between the two temperatures is the boiling range.
A third aspect of the invention provides the use of a phosphorus-containing compound as described above in a polymeric material.
The polymer material in the present application includes, but is not limited to, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, nylon, polycarbonate, polyurethane, polytetrafluoroethylene, polyethylene terephthalate, epoxy resin, phenolics, polyimide, melamine formaldehyde resin, natural rubber, butyl rubber, butadiene rubber, chloroprene rubber, ethylene propylene diene monomer rubber, acrylate rubber, urethane rubber, silicone rubber, fluororubber, nylon, dacron, acrylic polyester fiber, aramid fiber, polypropylene fiber.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
29g of dodecylphenol (CAS number: 27193-86-8), 58g of 200# solvent oil (boiling range: 140-200 ℃) are sequentially added into a 250ml three-neck flask, 22g of diphenyl phosphorus chloride (CAS number: 1079-66-9) and 22g of 200# solvent oil are uniformly mixed, then the mixture is slowly dripped into the three-neck flask under magnetic stirring at 120 ℃ for 1h, the reaction is continued for 2h at 120 ℃ after the dripping is finished, then the temperature is raised to 160 ℃ at 20 ℃/h, the temperature is kept at 160 ℃ for reaction for 4h, the temperature is continuously raised to 210 ℃, the distilled solvent is received during the period, the residual solvent and the excessive dodecylphenol raw material are distilled out in vacuum, 45.03g of light yellow transparent clear liquid product is obtained, and the product is shown as formula 6.
Formula 6:
Figure BDA0002821917870000071
example 2
31.7g of cardanol (CAS number: 501-24-6), 64g of 200# solvent oil (boiling range: 140-200 ℃) are sequentially added into a 250ml three-neck flask, 22g of diphenyl phosphorus chloride (CAS number: 1079-66-9) and 22g of 200# solvent oil are uniformly mixed, then the mixture is slowly dripped into the three-neck flask under magnetic stirring at 120 ℃ for 1h, the reaction is continued for 2h at 120 ℃ after the dripping is finished, then the temperature is increased to 160 ℃ at 20 ℃/h, the temperature is kept for reaction for 4h at 160 ℃, the temperature is continuously increased for 180 ℃, the evaporated solvent is received during the period of continuous temperature increase, the residual solvent and unreacted raw materials are evaporated in vacuum, 50.1g of yellow transparent clear liquid product is obtained, and the product is shown in formula 7.
Formula 7:
Figure BDA0002821917870000081
example 3
Sequentially adding 20g of isooctanol (CAS number: 104-76-7), 15g of triethylamine (CAS number: 121-44-8) and 40g of 120# solvent oil into a 250ml three-neck flask, uniformly mixing 22g of diphenyl-phosphorus chloride (CAS number: 1079-66-9) and 22g of 120# solvent oil, slowly dripping into the three-neck flask under magnetic stirring at the temperature of-5 ℃, continuously reacting for 2h at the temperature of-5 ℃, heating to 160 ℃ at 10 ℃/h, receiving the distilled triethylamine and solvent oil liquid, distilling out residual triethylamine, solvent oil and excessive isooctanol under reduced pressure at 160 ℃, cooling to room temperature, filtering, adding 2 times of 10 wt% sodium carbonate aqueous solution in volume of the filtrate, washing, separating, heating the oil phase to 105 ℃ for reduced pressure dehydration, cooling to 60 ℃, adding kieselguhr for filtering, obtaining 27.3g of light yellow transparent clear liquid product, the product is shown in formula 8.
Formula 8:
Figure BDA0002821917870000082
example 4
Adding 32.3g of dodecylphenol (CAS number: 27193-86-8) and 64g of 200# solvent oil (boiling range: 140-200 ℃) into a 250ml three-neck flask in sequence, uniformly mixing 10g of phenyl phosphorus dichloride (CAS number: 644-97-3) with 20g of 200# solvent oil, slowly dropwise adding into the three-neck flask under magnetic stirring at 120 ℃ for 1h, continuously reacting for 2h at 120 ℃ after dropwise adding, heating to 160 ℃ at 20 ℃/h, keeping the temperature for reacting for 4h at 160 ℃, continuously heating to 210 ℃, receiving the evaporated solvent during heating, and pulling vacuum to evaporate the excessive dodecylphenol raw material of the residual solvent to obtain 35.5g of a light yellow transparent clear liquid product, wherein the product is shown in formula 9.
Formula 9:
Figure BDA0002821917870000091
example 5
Adding 35.5g of cardanol (CAS number: 501-24-6) and 71g of 200# solvent oil (boiling range is 140-200 ℃) into a 250ml three-neck flask in sequence, uniformly mixing 10g of phenylphosphonium dichloride (CAS number: 644-97-3) with 22g of 200# solvent oil, slowly dripping into the three-neck flask under magnetic stirring at 120 ℃ for 1h, continuously reacting for 2h at 120 ℃ after dripping, heating to 160 ℃ at 20 ℃/h, keeping the temperature at 160 ℃ for reacting for 4h, receiving the distilled solvent during the reaction, and pulling vacuum to distill unreacted raw materials of the residual solvent to obtain 41.8g of a yellow transparent clear liquid product, wherein the product is shown as a formula 10.
Formula 10:
Figure BDA0002821917870000092
example 6
Sequentially adding 21.8g of isooctanol (CAS number: 104-76-7), 17g of triethylamine (CAS number: 121-44-8) and 44g of 120# solvent oil into a 250ml three-neck flask, uniformly mixing 10g of phenyl dichlorophosphate (CAS number: 644-97-3) with 20g of 120# solvent oil, slowly dripping into the three-neck flask under magnetic stirring at the temperature of-5 ℃ for 1h, continuously reacting at the temperature of-5 ℃ for 2h, heating to 60 ℃ at the temperature of 10 ℃/h, stirring and reacting for 2h, heating to 160 ℃ at the temperature of 20 ℃/h, receiving the steamed triethylamine and solvent oil liquid, distilling residual triethylamine, solvent oil and excessive isooctanol under reduced pressure at the temperature of 160 ℃, cooling to room temperature, filtering, adding 2 times of 10 wt% sodium carbonate aqueous solution in volume, washing, separating, heating the oil phase to 105 ℃ for reduced pressure dehydration, cooling to 60 ℃, adding kieselguhr for filtering, filtering to obtain light yellow transparent clear liquid product 17.6g, wherein the product is shown in formula 8.
Formula 11:
Figure BDA0002821917870000093
example 7
Adding 566g of dodecylphenol (CAS number: 27193-86-8) and 566g of No. 200 solvent oil (boiling range: 140-200 ℃) into a 2000 ml four-mouth bottle, and introducing N2Replacement, 82g of PCl is dripped under the condition of 60-70 DEG C3(CAS number: 7719-12-2) and 82g of a mixture of 200# solvent oil (boiling range: 140-200 ℃), after dropwise adding, heating to 180 ℃, carrying out heat preservation reaction until no obvious hydrogen chloride gas is generated, receiving the evaporated solvent during the reaction, continuously pulling vacuum until the pH value of tail gas is detected to be close to neutral and the acid value of the product is lower than 0.1mg/gKOH, and cooling to obtain 488 g of a yellowish transparent viscous clear liquid product, wherein the product is shown as a formula 12.
Formula 12:
Figure BDA0002821917870000101
example 8
613.1 g of cardanol (CAS number: 501-24-6) and 613g of 200# solvent oil (boiling range: 140-200 ℃) are added into a 2000 ml four-mouth bottle, and N is introduced2Replacement, 90g PCl is dripped under the condition of 60-70 DEG C3(CAS number: 7719-12-2) and 90g of 200# solvent oil (boiling range: 140-200 ℃), after dropwise adding, heating to 180 ℃, carrying out heat preservation reaction until no obvious hydrogen chloride gas is generated, receiving the distilled solvent, continuously pulling vacuum until the pH value of tail gas is detected to be close to neutral and the acid value of the product is lower than 0.1mg/gKOH, cooling to obtain 632.3 g of a light yellow transparent viscous liquid product, wherein the product is shown as a formula 13.
Formula 13:
Figure BDA0002821917870000102
comparative example 1
Comparative example 1 is a commercially available TNPP antioxidant (CAS number: 3050-88-2, trisnonylphenyl phosphite).
Comparative example 2
Comparative example 2 differs from example 1 in that 29g of dodecylphenol was replaced with 24.3g of nonylphenol (CAS number: 25154-52-3).
Evaluation of Performance
The performance tests of example 1, comparative examples 1-2, example 4 and example 7 are carried out, and the test contents comprise hydrolysis resistance tests and yellowing resistance tests.
1. And (3) hydrolysis resistance test: sample to water in a weight ratio of 1: 3 into a beaker, placed in an oven at 80 ℃, shaken evenly every 10min, the layer sample is taken to test the pH value and the time required for the pH value to drop below 3 is recorded, the results are shown in table 1.
2. And (3) yellowing resistance test: preparing a polyurethane sponge, wherein the formula of the polyurethane sponge is as follows: the composite material comprises, by weight, 100 parts of polyether polyol (PEG2000), 3 parts of water, 1 part of silicone oil, 330.2 parts of a foaming catalyst A, 90.15 parts of a tin catalyst T, 2 parts of a liquid phosphorus-containing compound and 43 parts of TDI. The sponge is aged for 72 hours at room temperature, cut into sponges with the thickness of 1cm, hung indoors, stained gray cards (GB/T251-2008) record yellowing series (the change series of the sealed light-proof storage sponge is 5) at different times, and the anti-yellowing effect of the phosphorus-containing compound is determined by the time required for the yellowing series of the sponges to be reduced to the same numerical value (the longer the time required is, the better the effect is).
TABLE 1
Examples Time required for pH value to drop to less than 3 The time required for the sponge to reach 4 levels of yellowing grade
Example 1 Greater than 24h 5 days
Comparative example 1 110min 2 days
Comparative example 2 Greater than 24h 5 days
Example 4 160min 3.5 days
Example 7 120min 1.5 days
According to the embodiment and the comparative example, the hydrolysis resistance of the partial liquid phosphorus-containing compound provided by the invention is obviously improved compared with that of the TNPP sold in the market, and the partial liquid phosphorus-containing compound has a very excellent effect on the yellowing resistance of the sponge, and the preparation raw material of the product does not contain nonylphenol, is more friendly to the environment and the human health and has a wide application prospect.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. The use of some numerical ranges in the claims also includes sub-ranges within their range, and variations in these ranges are also to be construed as being covered by the appended claims where possible.

Claims (10)

1. A liquid phosphorus-containing compound having a structure represented by formula 1, formula 1:
Figure FDA0002821917860000011
wherein R is1、R2、R3Each independently selected from phenyl or-O-R4，R4Is C8-C15 alkyl or a group of formula 2, formula 2:
Figure FDA0002821917860000012
wherein R is5Is C10-C18 alkyl or alkenyl; the liquid phosphorus-containing compound is a flowable liquid at room temperature.
2. The liquid phosphorus-containing compound of claim 1, wherein the alkyl group of C8-C15 is a straight chain alkyl group of C8-C15 or a branched chain alkyl group of C8-C15.
3. The liquid phosphorus-containing compound of claim 1, wherein the alkyl or alkenyl group of C10-C18 is a linear or branched structure of C10-C18.
4. The liquid phosphorus-containing compound of any one of claims 1 to 3, wherein R is1、R2、R3At least one of which is-O-R4。
5. The liquid phosphorus-containing compound of claim 1, which is prepared from a starting material comprising compound a represented by formula 3, formula 3:
Figure FDA0002821917860000013
wherein R is6、R7、R8Each independently selected from a halogen atom or a phenyl group;
the preparation raw materials also comprise a compound B shown as a formula 4, and the formula 4 is as follows:
Figure FDA0002821917860000014
wherein R is9Is C10-C18 alkyl or alkenyl.
6. Such as rightThe liquid phosphorus-containing compound of claim 5, wherein compound B is replaced with compound C according to formula 5, formula 5: r10-OH, wherein R10Is C8-C15 alkyl.
7. The liquid phosphorus-containing compound of claim 5, wherein R is6、R7、R8At least one of which is a halogen atom.
8. Use of a liquid phosphorus-containing compound according to any of claims 1 to 7 in a polymeric material.
9. A process for the preparation of the liquid phosphorus-containing compound according to claim 5, comprising the steps of: and (3) the molar ratio of the halogen atoms to the phenolic hydroxyl groups of the compound A to the compound B is 1: (1-1.5) carrying out the reaction.
10. A process for the preparation of the liquid phosphorus-containing compound according to claim 6, comprising the steps of: the molar ratio of the halogen atoms to the alcoholic hydroxyl groups of the compound A to the compound C is 1: (1-1.5) carrying out the reaction.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023166983A1 (en) * 2022-03-03 2023-09-07 住友化学株式会社 Phosphite ester composition

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3050499A (en) * 1958-03-24 1962-08-21 Nat Lead Co Stabilized vinyl halide resins
US3907939A (en) * 1969-06-16 1975-09-23 Ashland Oil Inc Phosphite esters of hindered phenols
US4126632A (en) * 1975-10-31 1978-11-21 Imperial Chemical Industries Limited Dimerization process
CN1089280A (en) * 1992-11-27 1994-07-13 赫彻斯特股份公司 Improved the cycloolefin polymer molding composition of stability to chemical degradation
CN1617764A (en) * 2001-11-26 2005-05-18 纳幕尔杜邦公司 Polymeric phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation of unsaturated nitriles
CN102089316A (en) * 2008-07-11 2011-06-08 巴斯夫欧洲公司 Liquid oxyalkylene bridged bis- and tris-phosphite ester mixtures
CN102471356A (en) * 2009-07-31 2012-05-23 科聚亚公司 Liquid alkylated trisaryl phosphite compositions having two alkyl groups with different carbon number
CN102718796A (en) * 2012-06-16 2012-10-10 南雄志一精细化工有限公司 Preparation method of novel environment-friendly phosphite ester antioxidant
CN108558942A (en) * 2018-04-03 2018-09-21 吉林市银联科技有限公司 A kind of bis-phenol list diphenylphosphite compound and preparation method
CN108586522A (en) * 2018-05-07 2018-09-28 山东省临沂市三丰化工有限公司 A kind of new bio base phosphite ester kind antioxidant and preparation method thereof
CN109776600A (en) * 2019-01-20 2019-05-21 南雄志一精细化工有限公司 An environmentally friendly liquid phosphite antioxidant

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3050499A (en) * 1958-03-24 1962-08-21 Nat Lead Co Stabilized vinyl halide resins
US3907939A (en) * 1969-06-16 1975-09-23 Ashland Oil Inc Phosphite esters of hindered phenols
US4126632A (en) * 1975-10-31 1978-11-21 Imperial Chemical Industries Limited Dimerization process
CN1089280A (en) * 1992-11-27 1994-07-13 赫彻斯特股份公司 Improved the cycloolefin polymer molding composition of stability to chemical degradation
CN1617764A (en) * 2001-11-26 2005-05-18 纳幕尔杜邦公司 Polymeric phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation of unsaturated nitriles
CN102089316A (en) * 2008-07-11 2011-06-08 巴斯夫欧洲公司 Liquid oxyalkylene bridged bis- and tris-phosphite ester mixtures
CN102471356A (en) * 2009-07-31 2012-05-23 科聚亚公司 Liquid alkylated trisaryl phosphite compositions having two alkyl groups with different carbon number
CN102718796A (en) * 2012-06-16 2012-10-10 南雄志一精细化工有限公司 Preparation method of novel environment-friendly phosphite ester antioxidant
CN108558942A (en) * 2018-04-03 2018-09-21 吉林市银联科技有限公司 A kind of bis-phenol list diphenylphosphite compound and preparation method
CN108586522A (en) * 2018-05-07 2018-09-28 山东省临沂市三丰化工有限公司 A kind of new bio base phosphite ester kind antioxidant and preparation method thereof
CN109776600A (en) * 2019-01-20 2019-05-21 南雄志一精细化工有限公司 An environmentally friendly liquid phosphite antioxidant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023166983A1 (en) * 2022-03-03 2023-09-07 住友化学株式会社 Phosphite ester composition

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