Method for preparing allyl alcohol copolymer based on intermediate conversion method, allyl alcohol copolymer and application of allyl alcohol copolymer

Abstract

The invention belongs to an allyl alcohol copolymer, and particularly relates to a method for preparing an allyl alcohol copolymer based on an intermediate conversion method, the allyl alcohol copolymer and application of the allyl alcohol copolymer. The method comprises the following steps: reacting allyl alcohol with a hydroxyl conversion reagent to convert hydroxyl into other groups so as to obtain a new allyl monomer; carrying out copolymerization on the monomer and other comonomers under the action of an initiator to obtain a copolymer; the hydroxyl is recovered by removing a conversion group, so that efficient and green preparation of the allyl alcohol copolymer is realized. The hydroxyl is converted into other groups, so that the reactivity rate of copolymerized monomers is closer during copolymerization, and the regulation and control of molecular weight and molecular composition are easy to realize; the high-temperature and high-pressure reaction conditions are avoided, and the safety risk caused by the fact that the highly toxic allyl alcohol raw material is greatly excessive is avoided; the polymerization reaction can be performed under normal pressure, the reaction condition is mild, and the equipment investment and maintenance cost are reduced; and the amount of residual allyl alcohol in the product is greatly reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to allyl alcohol copolymer, and particularly relates to a method for preparing allyl alcohol copolymer based on an intermediate conversion method, an allyl alcohol copolymer and application thereof. BACKGROUND

[0002] Allyl alcohol copolymer generally refers to a copolymer formed by allyl alcohol and other monomers such as styrene, acrylic ester, maleic anhydride, vinyl ether, etc., and is an important functional polymer material. Its core value lies in the combination of the adjustable hydroxyl content provided by the allyl alcohol monomer, the different copolymer structure, the strong adhesion given by the hydroxyl, etc., and has a wide range of applications in the fields of coatings, inks, biological materials, electronic packaging material preparation, etc. In addition, it can also be used as a precursor or macromonomer for synthesizing high-performance polymers, further preparing derivative resins, including aliphatic acid ester, alkyd resin, polyester, polyurethane rubber, and can be used as an ink carrier to change the hardness, viscosity, high gloss, and the rich hydroxyl can realize the application in the biological field through biomolecular coupling, biocompatibility crosslinking, casting into a film, preparing microspheres, fibers, scaffolds, hydrogels, etc. Unfortunately, in the preparation process of the allyl alcohol copolymer, there are a series of pain points.

[0003] The great difference in the properties of the comonomers poses a challenge to the copolymerization. Allyl alcohol has a low tendency of self-polymerization due to the conjugated structure formed by the double bond and the free radical, so the difference in the reactivity ratio between the copolymerization and the comonomer is large. For example, the reactivity ratio of styrene is much larger than that of allyl alcohol, so a large amount of styrene homopolymer is often obtained during copolymerization, and less copolymer is obtained, and the content of allyl alcohol unit in the obtained copolymer is much lower than the monomer ratio. In the actual process, the allyl alcohol monomer is usually greatly excessive, which leads to a very low conversion rate of allyl alcohol, or the styrene is slowly added at a later stage. This copolymerization path is difficult to obtain high molecular weight structure, high reaction pressure and high reaction temperature.

[0004] The primary hydroxyl group on the allyl alcohol molecule is prone to chain transfer reaction at high temperature and in a free radical environment, acting as a chain transfer agent to consume free radicals, which inhibits the growth of polymer molecular weight, resulting in low molecular weight and wide distribution of the product, and reduces the polymerization rate. The dehydration conversion mechanism of the hydroxyl group under the action of high temperature converts allyl alcohol into propylene aldehyde, which participates in crosslinking reaction to form insoluble gel to block the reactor. Propylene aldehyde and its subsequent oxidation products can change the composition of the copolymer, affecting the product purity and the preset function.

[0005] The production process has high risk. This reaction is carried out at high temperature (150-250℃) and high pressure, especially the highly toxic allyl alcohol is always excessive and exists in gas and liquid phases in the reactor, and the second monomer is continuously added under pressurized conditions, which puts high requirements on the process control.

[0006] The separation of unreacted allyl alcohol poses serious safety risks. Highly toxic allyl alcohol requires high-temperature distillation or solvent extraction to remove it from high-viscosity polymer mixtures. Its high volatility, high skin permeability, and flammability mean that acute poisoning can easily occur during operation through vapor inhalation or contact with leaked liquid, making it a key factor restricting safe production.

[0007] Allyl alcohol residue in products is also one of the challenges of current technology. Unless repeatedly purified, allyl alcohol is difficult to remove completely, which affects subsequent applications, especially in the biological and civilian fields.

[0008] In summary, the current challenges in producing allyl alcohol copolymers include: difficulty in increasing the molecular weight and controlling the unit structure ratio; low allyl alcohol conversion efficiency and high production costs; difficulty in completely removing residual allyl alcohol from the product; the involvement of allyl alcohol throughout the process, posing significant safety risks; and stringent process control conditions due to high-temperature and high-pressure polymerization. Therefore, a completely different technological system is needed to solve these problems. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention provides a method for preparing allyl alcohol copolymers based on intermediate conversion, the allyl alcohol copolymers, and their applications.

[0010] The technical solution provided by this invention is as follows: A method for preparing allyl alcohol copolymers based on intermediate conversion includes at least the following steps: 1) React allyl alcohol with a hydroxyl conversion reagent to obtain an allyl monomer with the hydroxyl group converted; 2) The allyl monomer obtained in step 1) is copolymerized with the polymeric monomer to obtain the precursor of the target product, which is used to prepare the allyl alcohol copolymer.

[0011] Furthermore, it also includes step 3): removing the hydroxyl conversion group from the target product precursor obtained in step 2) to release the hydroxyl group, and then purifying it to obtain the allyl alcohol copolymer.

[0012] Based on the above technical solution: The preparation method includes at least the step of first converting allyl alcohol and then copolymerizing it with other monomers; A hydroxyl conversion reagent is used, and the conversion group is easily removed in subsequent processes; The above preparation method first reacts allyl alcohol with a hydroxyl conversion reagent to obtain a new allyl monomer with converted hydroxyl groups. The obtained new monomer is then copolymerized with other monomers to obtain a precursor of the target product. This precursor is then dehydroxylated to release the hydroxyl groups, and further purified to obtain an allyl alcohol copolymer. If the conversion groups are present, the copolymer itself is a material with a specific function and can be used directly.

[0013] Specifically, in step 1), the selection of the hydroxyl conversion reagent includes, but is not limited to, halosilane, halogenated alkane, halogenated alkoxyalkane, acid anhydride, acyl chloride or aldehyde, etc., which can react with the hydroxyl group to form a siloxane, ether, ester bond, acetal, etc.

[0014] Specifically, in step 1), the amount of the hydroxyl conversion reagent is 1.0 to 1.2 times the molar amount of allyl alcohol, and the feeding mode is one-time addition or multiple additions.

[0015] Specifically, in step 1), the reaction temperature is 0-100℃, and the reaction time is 0.5-12h.

[0016] In the above technical solution, the specific conditions of the hydroxyl conversion process vary depending on the conversion reagent. The reaction temperature is usually 0-100℃, and the reaction pressure is normal pressure to the vaporization equilibrium pressure corresponding to the reaction temperature. The reaction time is about 0.5-12 hours, which varies depending on the reaction temperature and the reaction reagent.

[0017] Specifically, in step 2), the polymerizable monomer is selected from any one or a mixture of more than one of linear terminal olefin, terminal olefin with branched end, terminal olefin with cyclic structure, olefin with aromatic ring structure, N-vinyl monomer or halogenated olefin.

[0018] In the above technical solution, monomers that can copolymerize with new allyl monomers can participate in copolymerization to obtain a target precursor, and then the hydroxyl conversion group is removed to release the hydroxyl group, and further purification to obtain an allyl alcohol copolymer. The monomers that can copolymerize with the new allyl monomers can be one or more, and the target precursor is obtained, and then the hydroxyl conversion group is removed to release the hydroxyl group, and further purification to obtain an allyl alcohol copolymer.

[0019] Specifically, in step 2), the molar ratio of the allyl monomer to the total copolymer monomer is 3-60mol%, and the molar ratio of the polymerizable monomer to the total copolymer monomer is 40-97mol%.

[0020] Specifically, in step 2), the copolymerization can be initiated by heat, light or radiation. The heat initiator is a commonly used initiator, including organic peroxide initiator, inorganic peroxide initiator, azo initiator, redox initiator, etc. The amount of initiator is 0.5%-5% of the total weight of monomers, which is adjusted according to the designed molecular weight, the activity of the initiator, the reaction temperature, etc. The reaction temperature is 0-100℃, which is determined according to the type and amount of initiator. The radiation initiation polymerization mechanism can be initiated without initiator.

[0021] Specifically, in step 2), the polymerization method is solution polymerization or bulk polymerization by reversible addition-fragmentation chain transfer polymerization. The molecular weight of the copolymer can be effectively increased, and the molecular weight distribution of the obtained polymer is narrower.

[0022] Specifically, in a solvent environment, the conversion group of the hydroxyl group is removed by using a removal reagent. By chemical reaction, in different solvent environments, using acid or base reagents, the conversion group of the hydroxyl group is removed. The specific removal conditions are determined according to the different conversion reagents and the common removal conditions in organic chemistry.

[0023] Specifically, the purification is carried out by using the dissolution-precipitation method. Because the product obtained in the foregoing process contains various impurities, the product needs to be purified. The dissolution-precipitation method is usually used. First, toluene, xylene, tetrahydronaphthalene, tetrahydrofuran, dichloromethane, acetone, N,N-dimethylformamide, dimethyl sulfoxide, ethyl acetate, etc. are used, and the specific solvent used depends on the proportion of different monomers in the copolymer. After dissolution, the filtrate is precipitated by using methanol, ethanol, diethyl ether, and then centrifuged or filtered. According to the purity requirement of the product, the process is repeated 2-3 times, and then dried to obtain the product.

[0024] Hydroxyl conversion reaction The hydroxyl conversion reaction described in the present application is similar to the hydroxyl protection reaction in organic synthesis, and there is no other restriction on the specific conversion reaction, as long as the hydroxyl group can be converted into other groups, and the subsequent removal process can be smoothly carried out. Preferably, the conditions in the conversion process and the subsequent removal process are mild, low in cost, low in toxicity, easy to separate, and recyclable.

[0025] Common hydroxyl conversion reagents include silicon ethers: tert-butyl dimethyl chlorosilane, trimethyl chlorosilane, tert-butyl diphenyl chlorosilane, triisopropyl chlorosilane, tert-butyl diphenyl chlorosilane, triethyl chlorosilane, tributyl chlorosilane, butyl dimethyl chlorosilane, triphenyl chlorosilane, propyl dimethyl chlorosilane, methyl diphenyl chlorosilane, tert-butyl dimethyl silane trifluoromethanesulfonic acid silane, alkyl ether: benzyl bromide, p-methoxy benzyl chloride, trityl chloride, alkoxyl alkyl ether: methoxy methyl chloride, (trimethylsil) ethoxy methyl chloride, 2-(chloromethyl) tetrahydropyran, ester: acetic anhydride, acetyl chloride, benzoyl chloride, acetal / ketone: benzaldehyde dimethyl acetal.

[0026] The conditions of the hydroxyl conversion depend on the conversion reagent. When selecting the conversion reagent to react with the hydroxyl group, both the mildness of the reaction conditions and the mildness of the removal process should be considered to avoid damage to the structure of the final allyl alcohol copolymer. These processes depend on the steric hindrance of the conversion reagent and the type of the conversion reagent. The specific reaction conditions correspond to the reaction conditions of the commonly used hydroxyl protection reagents.

[0027] The amount of the hydroxyl conversion reagent is preferably 1.0 to 1.5 equivalents of allyl alcohol, more preferably 1.05 to 1.3 equivalents, and most preferably 1.1 to 1.2 equivalents.

[0028] Copolymerization reaction The present application copolymerizes the newly obtained allyl monomer after the hydroxyl conversion with other comonomers to obtain a precursor polymer of the target product.

[0029] The monomer unit used in the copolymerization is not particularly limited as long as it can be subjected to radical polymerization. Specific examples include linear terminal olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and 1-tricosene, terminal olefins having branched terminals such as 3-methyl-l-butene, 4-methyl-l-pentene, 3-methyl-l-pentene, 4,4-dimethyl-l-pentene, 3-methyl-l-heptene, 3-methyl-l-nonene, and 3-methyl-l-undecene, terminal olefins having cyclic structures such as cyclohexyl ethylene, 3-cyclohexyl-l-propene, 4-cyclohexyl-l-butene, decahydronaphthyl ethylene, and 4-vinyl-l-cyclohexene, olefins having structures containing aromatic rings such as styrene, halogenated styrene, α-methyl styrene, 3-nitro styrene, vinyl imidazole, 4-cyanostyrene, vinyl esters such as vinyl acetate and vinyl propionate, N-vinyl monomers such as N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl formamide, N-vinyl caprolactam, (meth)acrylates, halogenated olefins, acrylonitrile, and methacrylonitrile. The monomer actually participating in the polymerization can be one or more of these.

[0030] In the optimization of the ratio of the comonomers, the number of the structural units of allyl alcohol is preferably 3 to 60 mol%, more preferably 5 to 40 mol%, and particularly preferably 10 to 30 mol% of the total number of the structural units. If the amount of allyl alcohol is less than 5 mol%, the hydroxyl value of the obtained copolymer is too low, and if it is more than 50 mol%, the viscosity of the copolymer is too large.

[0031] The copolymerization reaction can be performed in a solvent. Specific examples include toluene, benzene, t-butyl benzene, acetone, dichloromethane, chloroform, chlorobenzene, and dimethylformamide. These can be used alone or in combination of two or more.

[0032] The copolymerization reaction can be initiated by free radicals generated by heat, UV, electron beam, radiation, etc. The polymerization reaction can use traditional free radical polymerization, or can use RAFT (Reversible Addition-Fragmentation Chain Transfer) controlled free radical copolymerization technology. RAFT technology can extend the polymerization time and maintain the active chain end, so that the low activity monomer (such as allyl structural monomer) has more opportunities to participate in the reaction, thereby increasing its apparent proportion in the copolymer. Compared with traditional free radical polymerization, the chain transfer reaction of allyl monomer will cause a significant decrease in molecular weight, while RAFT inhibits chain termination through reversible chain transfer, which can significantly increase the molecular weight.

[0033] In the process of RAFT polymerization, the commonly used chain transfer agent (CTA) structures include: dithioesters such as benzyl dithiobenzoate, cumyl dithiobenzoate, 2-(dodecyltrithiocarbonato)-2-methylpropionic acid; trithiocarbonates such as benzyl trithiocarbonate, bis(thiobenzoyl) disulfide, 2-cyano-2-propyl dodecyltrithiocarbonate; dithiourethanes such as N,N-diethyldithiobenzyl carbamate; xanthates such as oxycarbonylmethyl S-benzyl xanthate. The amount of chain transfer agent is usually 1 / 10-1 / 300, preferably 1 / 20-1 / 200, more preferably 1 / 30-1 / 100, of the number of moles of monomer, depending on the design requirements of the molecular weight.

[0034] Examples of the thermal radical initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(isobutyrate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4,4-trimethylpentane); ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide; diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, and lauryl peroxide; dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide; peroxy ketones such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-di-t-butylperoxy cyclohexane, and 2,2-di-t-butylperoxy butane; alkyl peroxy esters such as t-butyl peroxy pivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy isobutyrate, di-t-butyl peroxy hexahydro-p- benzenedicarboxylate, di-t-butyl peroxy nonanedioate, t-butyl peroxy-3,5,5- trimethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy-2- ethylhexanoate, t-butyl peroxy acetate, t-butyl peroxy benzoate, di-t-butyl peroxy trimethyladipate, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy laurate, and t-hexyl peroxy benzoate; peroxy carbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and t-butyl peroxyisopropylcarbonate. The specific application is not limited to these examples, and they can be used alone or in combination of two or more.

[0035] Examples of the initiator for UV, electron beam, or radiation-induced polymerization include phenylacetone derivatives such as phenylacetone, 2,2-dimethoxy-2-phenylphenylacetone, diethoxyphenylacetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone derivatives such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-trimethylsilylbenzophenone, and 4-benzoyl-4'-methyl diphenyl sulfide; benzoin derivatives such as benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; methyl phenacylformate, benzoin dimethyl ketal, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. The specific application is not limited to these examples, and they can be used alone or in combination of two or more.

[0036] The amount of the initiator used varies depending on the reaction temperature and the composition ratio of the monomers, and cannot be generalized. Generally, the amount of the initiator used is preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass.

[0037] The polymerization temperature can be determined depending on the type of the polymerization initiator. In the case of UV-induced polymerization, room temperature can be used, and in the case of thermal polymerization, the reaction temperature is preferably appropriately determined depending on the decomposition temperature of the initiator, and is generally preferably 50°C to 150°C, and particularly preferably 70°C to 130°C. If the temperature is low, the reaction rate is low, and if the temperature is high, chain transfer can be induced, thereby reducing the molecular weight of the copolymer.

[0038] Reaction for removing the conversion group Depending on the type of the conversion group, a different removal process is adopted. The removal process conditions should be selected so as to avoid degradation of the copolymer, destruction of the structure, participation of other groups in the reaction, and the like.

[0039] After the completion of the reaction, the allyl alcohol copolymer as a reaction product is isolated by known operations and treatments such as neutralization, solvent extraction, washing with water, liquid separation, distillation of the solvent, and reprecipitation.

[0040] The present application also provides an allyl alcohol copolymer prepared by the above-described method.

[0041] The allyl alcohol copolymer of the present application contains a structure represented by Formula (1) and Formula (2) as a monomer unit.

[0042] In Formula (2), R1and R2each represent -H, an aliphatic group, an ester group, an amide group, a halogenated group, a group containing an aromatic structure, or the like.

[0043] The method for preparing an allyl alcohol copolymer described above includes at least a step of subjecting an allyl alcohol to a conversion reaction in advance.

[0044] The allyl alcohol copolymer described above can contain different structures of Formula (2) as a monomer unit.

[0045] The allyl alcohol copolymer described above can contain a structure of Formula (2) in which R1and R2are the same as the molecular formula of a monomer as a monomer unit.

[0046] The allyl alcohol copolymer according to any one of the above-described embodiments can contain a monomer unit represented by Formula (1) in an amount of 3 to 60 mol%, and a monomer unit represented by Formula (2) in an amount of 40 to 97 mol%.

[0047] The allyl alcohol copolymer according to the above description, wherein the hydroxyl value is in the range of 10 to 300 mgKOH / g.

[0048] The allyl alcohol copolymer according to the above description, wherein the number average molecular weight is in the range of 500 to 20,000.

[0049] According to the present invention, an allyl alcohol copolymer can be effectively produced. The allyl alcohol copolymer produced by the present invention has both a polar group and a hydrophobic group, has excellent compatibility and adhesion with various resins, has excellent electric insulating properties, low water absorption, thermal stability and surface activity, and can be used as a resin modifier, a coating agent component, an ink, an adhesive and a primer, a high-performance wax, a compatibilizer, a surfactant, a grease additive, a polyurethane material and a polyester material.

[0050] Allyl alcohol copolymer The allyl alcohol copolymer of the present invention comprises a structure represented by formula (1) and (2) as a monomer unit.

[0051] In formula (2), R1may be -H, a methyl group, an ethyl group, -X (X is a halogen atom).

[0052] In formula (2), R2may be H, an aliphatic group, an ester group, an amido group, a halogenated group, a group containing an aromatic structure, and the like.

[0053] The copolymer of the present invention is not limited otherwise, as long as it comprises a structure represented by formula (1) and (2).

[0054] If necessary, two or more kinds of such third monomer units can be introduced.

[0055] The copolymer of the monomer unit represented by formula (1) and the monomer unit represented by formula (2) can be a random, block or alternating copolymer, depending on the polymerization conditions. A random mode is preferred, and the same applies to the case where the copolymer comprises a third monomer unit.

[0056] The proportion of each monomer unit in the final polymer can be controlled by adjusting the proportions of the two monomer units. It is preferred that the first allyl alcohol monomer unit accounts for 3 to 60 mol% of the total monomer units, more preferably 5 to 40 mol%, and most preferably 10 to 30 mol%.

[0057] According to the requirements of the actual application, it is preferred that the hydroxyl value of the allyl alcohol copolymer of the present invention is 10 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, and most preferably 100 to 230 mgKOH / g.

[0058] The molecular weight of the copolymer of the present application is 500-20000, preferably 500-8000, more preferably 600-5000, and most preferably 700-4000, according to the requirements of practical application.

[0059] The present application also provides the use of the allyl alcohol copolymer for preparing resin modifier, coating agent, ink, adhesive, primer, wax, compatibilizer, surfactant, grease additive, polyurethane material or polyester material.

[0060] The present application has the following advantages: The present application converts the hydroxyl group into other groups by reacting the allyl alcohol with a hydroxyl group conversion reagent, to obtain a new allyl monomer; the monomer is then copolymerized with other comonomers under the action of an initiator, to obtain a copolymer; and then the conversion group is removed to restore the hydroxyl group, to realize the efficient and green preparation of the allyl alcohol copolymer; if the conversion group exists, the copolymer itself is a certain special functional material, which can be directly used.

[0061] In the present application, the hydroxyl group is converted into other groups, so that the reactivity of the copolymerized monomers is closer during the implementation of the copolymerization, the molecular weight and molecular composition are easy to control, the high-temperature and high-pressure reaction conditions are avoided, the safety risk caused by the large excess of the toxic allyl alcohol raw material is avoided, the polymerization reaction can be carried out under normal pressure, the reaction conditions are mild, the equipment investment and maintenance cost are reduced, the amount of residual allyl alcohol in the product is greatly reduced, and multiple grades of products can be conveniently prepared, so that the product quality competitiveness is enhanced. The resin copolymer obtained by the present application has wide compatibility and excellent adhesion, and has wide application in the fields of resin modifier, coating, ink, adhesive, high-performance wax, compatibilizer, surfactant, grease additive, polyurethane material, polyester material, biological material, etc.

[0062] In the present application, the conversion rate of the allyl alcohol can be as high as 72.8%. DETAILED DESCRIPTION

[0063] The principles and features of the present application are described below, and the examples are only used to explain the present application, and are not used to limit the scope of the present application.

[0064] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges or values should be construed to be approximations that allow for significant variation. Various ranges of values that are explicitly delineated in the specification as supplied herein constitute each individual value within the range and all sub-ranges of values within the range. For numerical ranges expressed in the format "from X to Y," "X to Y," or "X / Y," "X" and "Y" are each individually a numerical value that can be expressed as a range of values. Furthermore, a numerical value can be expressed as a range of values using both the "phr" and the "wt%" format. For example, a value of 10 wt% can be expressed as a range of values of 10 phr to 10 wt%.

[0065] The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents, etc. used are commercially available reagents and materials unless otherwise specified.

[0066] Example 1 Under dry nitrogen protection, 140 mL of anhydrous pyridine was added into a 1 L three-necked flask, ice water cooling (0-5°C), 29 g of allyl alcohol was slowly added dropwise while stirring. 40 mL of acetyl chloride was diluted with 40 mL of dichloromethane, and was slowly added dropwise into the reaction system (~40 minutes, temperature control ≤10°C), and the tail gas was absorbed by 10% NaOH solution. After dropping, it was stirred for 30 minutes, and then it was continued to react at room temperature for 3 hours. The reaction solution was poured into 700 mL of ice water to quench, and was extracted with 150 mL of dichloromethane three times, and the combined organic phase was washed with 300 mL of 5% HCl, 300 mL of saturated NaHCO3 and 300 mL of saturated brine successively, and was dried with 30 g of anhydrous MgSO4, and then the solvent was removed by rotary evaporation. 43 g of allyl acetate was obtained by vacuum distillation.

[0067] The RAFT (Reversible Addition-Fragmentation Chain Transfer) controlled radical copolymerization technology was used. 20 g of allyl acetate, 1.3 g of CPDB (2-cyano-2-propyl benzodithiole) and 0.25 g of AIBN (azobisisobutyronitrile) were dissolved in 70 mL of anhydrous toluene, and were transferred into a 250 mL Schlenk reaction flask. 10.4 g of styrene was dissolved in 30 mL of anhydrous toluene, and the styrene solution was slowly added into the reaction flask under N2 atmosphere and stirring at 70°C for 6 hours, and the reaction was continued for 24 hours. After the reaction was completed, the viscous solution was cooled to room temperature, and was added dropwise into 1 L of chilled methanol under stirring to precipitate the copolymer. The white solid obtained was filtered, washed with 50 mL of cold methanol twice, and was dried at 40°C under vacuum for 24 hours, to obtain about 16 g of copolymer.

[0068] 15 g of the copolymer was dissolved in 150 mL of tetrahydrofuran, 3.5 g of potassium hydroxide was dissolved in 75 mL of methanol, and the latter was added into the former, and was reacted at 50°C constant temperature and stirring for 6 hours, and then it was cooled to room temperature, and 10% HCl aqueous solution was slowly added dropwise under stirring until the pH was 7, and then the obtained solution was dialyzed in a dialysis bag with a molecular weight cut-off of 500 Da, and was rotary evaporated below 40°C to dryness, to obtain 12.5 g of poly(allyl alcohol-styrene) copolymer, with a number average molecular weight of 4500 and a hydroxyl value of 210 mg / g KOH.

[0069] Example 2 Into a 1 L three-necked flask, 140 mL dry pyridine was added as solvent and acid binding agent, ice water cooling (0-5 °C), 29 g allyl alcohol was added slowly dropwise under stirring. 40 mL acetyl chloride was diluted with 40 mL dichloromethane, which was added slowly dropwise into the reaction system (~ 40 min, temperature control ≤ 10 °C), and the tail gas was absorbed by 10% NaOH solution. After dropwise addition, stirring was continued for 30 min, and the reaction was continued at room temperature for 3 h. The reaction solution was poured into 700 mL ice water to quench, and extracted with 150 mL dichloromethane three times. The organic phase was combined and washed with 300 mL 5% HC1, 300 mL saturated NaHC03 and 300 mL saturated brine successively, and dried with 30 g anhydrous MgS04, and then the solvent was removed by rotary evaporation. 43 g of allyl acetate was obtained by vacuum distillation.

[0070] 20 g of allyl acetate and 0.6 g of AIBN (azobisisobutyronitrile) were dissolved in 60 mL of anhydrous toluene and transferred to a 250 mL Schlenk reaction flask. 10.4 g of styrene was dissolved in 40 mL of anhydrous toluene, and the styrene solution was slowly added to the reaction flask under N2atmosphere at 70 °C for 6 h under stirring. The reaction was continued for 24 h. After the reaction was completed, the viscous solution was cooled to room temperature, and then added dropwise to 1 L of chilled methanol under stirring to precipitate the copolymer. The white solid obtained was filtered, washed twice with 50 mL of cold methanol, and dried at 40 °C under vacuum for 24 h to obtain about 14 g of copolymer.

[0071] 10 g of the copolymer was dissolved in 100 mL of tetrahydrofuran, and 2.5 g of potassium hydroxide was dissolved in 50 mL of methanol. The latter was added to the former, and the reaction was carried out at 50 °C for 6 h under constant temperature stirring. The solution was cooled to room temperature, and 10% HC1 aqueous solution was slowly added dropwise under stirring until the pH was 7. The obtained solution was dialyzed in a dialysis bag with a molecular weight cutoff of 500 Da, and then rotary evaporated at 40 °C or below to obtain 7.5 g of poly(allyl alcohol-styrene) copolymer. The number average molecular weight of the copolymer was 3500, and the hydroxyl value was 185 mg / g KOH.

[0072] Example 3 In a dry, N2 purged reactor, 400 ml of fresh dry THF was added, followed by 29 g of allyl alcohol. To the stirring solution of allyl alcohol in THF, 60 g of anhydrous imidazole was added in one portion. 90 g of t-butyldimethylsilyl chloride was dissolved in 100 ml of THF, and was added slowly into the reactor under N2 atmosphere in an ice bath, keeping the temperature at 0-10°C, and the reaction was allowed to proceed for 3 hours. The ice bath was removed, and the temperature was allowed to rise to room temperature, and the reaction was allowed to proceed for another 2 hours. After the reaction, 150 ml of water was added slowly to quench the reaction, and the mixture was transferred to a separatory funnel, and 150 ml of ethyl ether was used as the extracting agent, and the organic phase was collected after shaking and phase separation. The organic phase was washed with 150 ml of saturated NaHCO3 solution, and 150 ml of saturated NaCl solution, and the organic phase was dried with anhydrous MgSO4 for 30 minutes. The drying agent was removed by filtration, and the organic solvent was removed by rotary evaporation, and 76 g of the product (TBS-allyl ether) was obtained.

[0073] The RAFT (Reversible Addition-Fragmentation Chain Transfer) controlled radical copolymerization technique was used. In a dry reaction flask, 70 ml of anhydrous toluene, 34.4 g of TBS-allyl ether, 1.3 g of 2-cyano-2-propyl benzodithiole, and 0.25 g of initiator (AIBN, azobisisobutyronitrile) were added in sequence. The reaction flask was purged with N2, and was stirred in a 65°C constant temperature oil bath. 10.4 g of styrene, from which the polymerization inhibitor was removed by pre-distillation under reduced pressure, was dissolved in 30 ml of anhydrous toluene, and the latter was added slowly into the former in 6 hours, and the reaction was allowed to proceed for 24 hours. After cooling, the post-polymerization product was added into 700 ml of methanol to obtain a flocculent precipitate, which was filtered, washed with cold methanol three times, and dried under vacuum to obtain a white or light yellow solid 20 g.

[0074] The dried 20 g of polymer was dissolved in anhydrous THF to prepare a 15 wt% solution, and 75 ml of 1.0 M TBAF (tetra-n-butylammonium fluoride) THF solution was added slowly dropwise under N2 protection and ice bath cooling. After the dropwise addition was completed, the ice bath was removed, and the reaction was stirred at room temperature for 2 hours. During the reaction, white fluorosilicate precipitate was observed. The mixture was poured into ice water, and the polymer was extracted with ethyl acetate three times. The organic phase was washed with saturated ammonium chloride solution to neutralize residual fluoride ions, and then with deionized water until neutral. The organic phase was dried with anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The viscous material was re-dissolved in a small amount of THF, and was precipitated into cold methanol / water (1:1) for purification. After filtration and vacuum drying, 13 g of styrene-allyl alcohol copolymer was obtained, which had a number average molecular weight of 6100 and a hydroxyl value of 235 mg / g KOH.

[0075] Example 4 Into a 1 L three-necked flask, 140 mL dry pyridine was added under nitrogen protection, ice-water cooling (0-5°C), 29 g allyl alcohol was added dropwise slowly under stirring. 40 mL acetyl chloride was diluted with 40 mL dichloromethane, which was added dropwise into the reaction system (40 min, temperature control ≤10°C), the tail gas was absorbed by 10% NaOH solution. After dropping, it was stirred for 30 min, and then the temperature was raised to room temperature for 3 h. The reaction solution was poured into 700 mL ice water for quenching, extracted with 150 mL dichloromethane three times, the organic phase was combined and washed with 300 mL 5% HCl, 300 mL saturated NaHCO3 and 300 mL saturated brine successively, dried with 30 g anhydrous MgSO4, and then the solvent was removed by rotary evaporation. 43 g of allyl acetate was obtained by vacuum distillation.

[0076] The RAFT (Reversible Addition-Fragmentation Chain Transfer) controlled radical copolymerization technology was used. 20 g of allyl acetate, 1.3 g of CPDB (2-cyano-2-propyl benzodithiole) and 0.25 g of AIBN (azobis isobutyronitrile) were dissolved in 70 mL of anhydrous toluene, and then transferred to a 250 mL Schlenk reaction flask. 6.24 g of styrene was dissolved in 30 mL of anhydrous toluene, and then the styrene solution was slowly added into the reaction flask under N2 atmosphere and stirring at 70°C for 6 h. The reaction was carried out for 24 h. After the reaction was completed, the viscous solution was cooled to room temperature, and then added dropwise into 1 L of chilled methanol under stirring to precipitate the copolymer. The white solid was filtered, washed with 50 mL of cold methanol twice, and then dried at 40°C under vacuum for 24 h to obtain about 9.0 g of copolymer.

[0077] 9.0 g of the copolymer was dissolved in 150 mL of tetrahydrofuran, and 3.5 g of potassium hydroxide was dissolved in 75 mL of methanol. The latter was added into the former, and then the reaction was carried out under constant temperature stirring at 50°C for 6 h. The solution was cooled to room temperature, and then 10% HCl aqueous solution was added dropwise slowly under stirring until the pH was 7. The obtained solution was dialyzed in a dialysis bag with a molecular weight cutoff of 500 Da, and then rotary evaporated at 40°C or below to obtain 8.0 g of poly(allyl alcohol-styrene) copolymer. The number average molecular weight of the copolymer was 4500, and the hydroxyl value was 225 mg / g KOH.

[0078] Example 5 Into a 1 L three-necked flask, 140 mL dry pyridine was added under nitrogen protection, ice-water cooling (0-5℃), 29 g allyl alcohol was added dropwise slowly under stirring. 40 mL acetyl chloride was diluted with 40 mL dichloromethane, which was added dropwise into the reaction system slowly (~40 min, temperature control ≤10℃), the tail gas was absorbed by 10% NaOH solution. After dropping, it was stirred for 30 min, and then the temperature was raised to room temperature for 3 h. The reaction solution was poured into 700 mL ice water for quenching, and extracted with 150 mL dichloromethane for three times. The organic phase was combined and washed with 300 mL 5% HCl, 300 mL saturated NaHCO3 and 300 mL saturated brine successively, and then dried with 30 g anhydrous MgSO4, and the solvent was removed by rotary evaporation. 43 g allyl acetate was obtained by vacuum distillation.

[0079] The RAFT (Reversible Addition-Fragmentation Chain Transfer) controlled radical copolymerization technology was used. 20 g allyl acetate, 1.3 g CPDB (2-cyano-2-propyl benzodithiole) and 0.25 g AIBN (azobisisobutyronitrile) were dissolved in 70 mL anhydrous toluene, and then transferred into a 250 mL Schlenk reaction bottle. 11 g cyclohexyl ethylene was dissolved in 30 mL anhydrous toluene, and then the styrene solution was slowly added into the reaction bottle under N2 atmosphere and stirring at 70℃ for 6 h, and the reaction was carried out for 24 h. After the reaction was completed, the viscous solution was cooled to room temperature, and then added dropwise into 1 L chilled methanol under stirring to precipitate the copolymer. The white solid was filtered, washed with 50 mL cold methanol twice, and then dried at 40℃ under vacuum for 24 h to obtain about 15 g copolymer.

[0080] 15 g copolymer was dissolved in 150 mL tetrahydrofuran, and 3 g potassium hydroxide was dissolved in 75 mL methanol, and then the latter was added into the former, and then the reaction was carried out under constant temperature stirring at 50℃ for 6 h. After cooling to room temperature, 10% HCl aqueous solution was slowly added dropwise under stirring until the pH value was 7. The obtained solution was dialyzed in a dialysis bag with a molecular weight cut-off of 500 Da, and then rotary evaporated at 40℃ or below to obtain 12.5 g poly(allyl alcohol-styrene) copolymer. The number average molecular weight of the copolymer was 5000, and the hydroxyl value was 215 mg / g KOH.

[0081] The above only describes the preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing allyl alcohol copolymers based on intermediate conversion, characterized in that, At least the following steps are included: 1) React allyl alcohol with a hydroxyl conversion reagent to obtain an allyl monomer with the hydroxyl group converted; 2) Copolymerize the allyl monomer obtained in step 1) with other polymerizable monomers to obtain the precursor of the target product.

2. The method for preparing allyl alcohol copolymers based on intermediate conversion according to claim 1, characterized in that, In step 1): The selection of hydroxyl conversion reagents includes, but is not limited to, halosilanes, haloalkanes, haloalkoxanes, acid anhydrides, acyl chlorides, or aldehydes; The amount of hydroxyl conversion reagent used is 1.0 to 1.2 times the molar amount of allyl alcohol, and it can be added at once or in several portions.

3. The method for preparing allyl alcohol copolymers based on intermediate conversion according to claim 1, characterized in that, In step 1): The reaction temperature is 0℃-100℃; The reaction time is 0.5-12 hours.

4. The method for preparing allyl alcohol copolymers based on intermediate conversion according to claim 1, characterized in that, In step 2): The other polymerizable monomers are selected from any one or a mixture of straight-chain terminal olefins, terminal olefins with branched ends, terminal olefins with cyclic structures, olefins with aromatic ring structures, N-vinyl monomers, or halogenated olefins. The allyl monomer accounts for 3-60 mol% of the total copolymer monomers. Other polymeric monomers account for 40-97 mol of the total copolymer monomers.

5. The method for preparing allyl alcohol copolymers based on intermediate conversion according to claim 1, characterized in that, In step 2): The copolymerization adopts thermal initiation, photoinitiation or radiation initiation polymerization mechanism. The amount of initiator used is 0.5%-5% of the total weight of allyl monomer and other polymeric monomers, and the reaction temperature is 0℃-100℃. The copolymerization method is solution polymerization or bulk polymerization using reversible addition-fragmentation chain transfer polymerization.

6. The method for preparing allyl alcohol copolymers based on intermediate conversion according to any one of claims 1 to 5, characterized in that, It also includes step 3): removing the hydroxyl conversion group from the target product precursor obtained in step 2) to release the hydroxyl group, and then purifying it to obtain the allyl alcohol copolymer.

7. The method for preparing allyl alcohol copolymers based on intermediate conversion according to claim 6, characterized in that: In a solvent environment, a dehydrogenating reagent is used to remove the hydroxyl group and convert it. Purification was performed using a dissolution-precipitation method.

8. An allyl alcohol copolymer, characterized in that: Prepared according to the method of claim 6 or 7.

9. The allyl alcohol copolymer according to claim 8, characterized in that: Molecular weight ranges from 500 to 20,000; Its hydroxyl value is between 10-300 mg KOH / g.

10. An application of the allyl alcohol copolymer according to claim 8 or 9, characterized in that: Used in the preparation of resin modifiers, coating agents, inks, adhesives, primers, waxes, compatibilizers, surfactants, grease additives, polyurethane materials, or polyester materials.

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