CN104610515A - Reactive group-contained comb-type graft copolymer, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a comb-shaped graft copolymer containing reactive groups, a preparation method and application thereof. Small molecular monomer A and macromolecular monomer B are copolymerized to form a comb graft copolymer whose main chain is small molecular monomer A and side chain is macromonomer B; the weight of macromolecular monomer B is the comb graft copolymer The weight of the small molecular monomer A is 99.9wt% to 20wt% of the mass of the comb-shaped graft copolymer. The copolymer of the present invention is a comb-shaped graft copolymer with reactive groups in the side chain, and can be used as a compatibilizer and a chain extender.

Description

A comb-shaped graft copolymer containing reactive groups and its preparation method and application

technical field

The invention belongs to the field of polymer materials, and relates to a comb-shaped graft copolymer containing reactive groups and its preparation method and application, in particular to a comb-shaped polymethyl (meth)acrylate containing reactive groups and its Preparation methods and applications.

Background technique

Comb graft copolymers are composed of two different polymer chains connected by chemical bonds. One of them is a polymer backbone (skeleton) composed of A units, that is, the main chain; the other is a polymer branch composed of B units, that is, side chains. There are three ways to combine side chains to the main chain through covalent bonds, namely Graft to, Graft through and Graft from. The so-called Graft through method is to first synthesize the side chain of the macromolecule, and use the polymerization method to polymerize the macromonomer with double bonds or other reactive groups at the end to prepare the comb-shaped graft polymer. The advantage of the Graft through method is that it can well control the graft density and structural integrity of the comb graft polymer.

The development of modern science and technology requires polymer materials to have various and high comprehensive properties. For example, certain plastics are required to be both high temperature resistant and easy to form and process; both high strength and good toughness are required; both excellent mechanical properties and certain special functions are required. Obviously, a single high polymer is difficult to meet these high-performance requirements. At the same time, it is not easy to develop a brand-new material, which is not only time-consuming and costly, but also quite difficult; in contrast, it is not only simple and convenient to use existing polymer materials for blending modification to prepare high-performance materials Effective and quite economical too. Since the 1960s, polymer blending modification technology has developed rapidly. Through the blending of various polymers, the characteristics of different polymers are optimized and combined, so that the material properties are significantly improved, or endowed with original polymers. It has a new performance, which opens up a broad way for the development and utilization of polymer materials.

Polymer alloy is a composite system composed of two or more polymer materials, specifically, it is composed of two or more different types of resins, or resin and a small amount of rubber, or resin and a small amount of thermoplastic elastomer, Composite system prepared by blending in molten state. However, most polymer alloys are incompatible systems. In order to obtain practical polymer alloy materials, it is necessary to control the morphology and interface modification of incompatible polymer systems. Reactive compatibilizers rely on their own reactive groups to react with other polymer components to form chemical bonds to achieve compatibilization. Therefore, the key to its preparation is how to introduce highly active reactive functional groups into the polymer. The simpler method is Using appropriate chemical reactions, the polymer main chain, side chains or end groups are equipped with reactive groups.

The applicant discloses a comb-shaped graft polymer containing reactive groups and its preparation method and application in the patent CN 103421154 A. In this patent, the reactive group is located on the main chain of the molecule. During the reactive blending process, the chemical reaction between the reactive group and the complementary group is interfered by the steric effect of the grafted side chain.

Contents of the invention

An object of the present invention is to provide a kind of comb-shaped graft copolymer containing reactive group for the deficiencies in the prior art, specifically, the comb-shaped polymethyl (meth)acrylate that side chain contains reactive group .

The multipolymer of the present invention is the comb-shaped graft copolymer that main chain is micromolecular monomer A, side chain is macromolecular monomer B; The weight of macromolecular monomer B is 0.1wt%～of comb-shaped graft copolymer quality 80wt﹪, the weight of the small molecule monomer A is 99.9wt﹪～20wt﹪ of the mass of the comb-shaped graft copolymer;

The number average molecular weight of the comb graft copolymer is 5000～100000;

As preferably, the weight of the small molecular monomer A is 80wt% to 50wt% of the quality of the comb-shaped graft copolymer;

As preferably, the weight of macromolecular monomer B is 5wt%～50wt% of comb graft copolymer quality;

As preferably, the number average molecular weight of the comb graft copolymer is 15000～60000;

Described macromonomer B is represented by general formula (1):

Wherein R ₁ and R ₂ are a hydrogen atom or a methyl group, R ₃ is a methyl group, an ethyl group, a butyl group, a tert-butyl group or a glycidyl group, R ₄ is a hydrogen atom or a sec-butyl group, and X represents -CH ₂ CH( OH)CH ₂ -or -Z-NHCO-, Y is -L ₁ -L ₂ -S-, Z is -(CH ₂ CH ₂ O) _a (CH ₂ ) _b -, L ₁ is a direct bond, - O-, -COO- or -NH-, L ₂ is a C1~C20 alkylene group or a C6~C20 aryl group, S represents a sulfur atom, n is an integer from 5 to 100, m is 0 or 1, a is 0~ An integer of 20, b is an integer of 1 to 20;

The small molecule monomer A is one or more of methacrylate, acrylate, hydroxyl-containing ester, methacrylamide, unsaturated nitrile, styrene monomer and derivatives thereof.

The number average molecular weight of the macromonomer B is 500-10000.

Another object of the present invention is to provide a kind of preparation method of the comb-shaped graft copolymer containing reactive group, this method is that small molecular monomer A and macromolecular monomer B are copolymerized and form main chain to be small molecular monomer A , The side chain is the comb-shaped graft copolymer of macromonomer B; the addition of macromonomer B is 0.1wt﹪～80wt﹪ of the quality of comb-shaped graft copolymer, and the addition of small molecule A is 99.9wt% to 20wt% of the mass of the comb-shaped graft copolymer.

The number average molecular weight of the comb-shaped graft copolymer is 5,000-100,000.

The copolymerization method can be bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which is a mature technology in the prior art.

In the bulk polymerization method, the following method is adopted: under the protection of nitrogen, the polymerization initiator-1, the chain transfer agent, the small molecular monomer A, and the macromolecular monomer B are mixed and reacted at 50-120°C for 1-10 hours , to obtain a comb-shaped graft copolymer.

Described polymerization initiator-1 is all oil-soluble initiators.

The chain transfer agent is dodecyl mercaptan, mercaptoethanol, 3-mercaptopropanol, thioglycolic acid, mercaptomalic acid, isooctyl thioglycolate, n-butyl 3-mercaptopropionate or ethylene glycol dimercaptoacetate. alcohol esters.

The mass ratio of macromonomer B to the total amount of small molecule A and macromonomer B is 0.1 to 80:100; the mass ratio of oil polymerization initiator-1 to the total amount of small molecule A and macromonomer B The mass ratio is 0.001-5:100; the molar ratio of the chain transfer agent to the polymerization initiator-1 is 0.1-10:1.

In the solution polymerization method, the following method is adopted: under the protection of nitrogen, dissolve the polymerization initiator-2, chain transfer agent, small molecular monomer A, and macromolecular monomer B in an organic solvent, and react at 50-120°C 1 to 10 hours.

The polymerization initiator-2 can be a water-soluble or oil-soluble initiator, the water-soluble initiator is all water-soluble initiators, and the oil-soluble initiator is all oil-soluble initiators.

The chain transfer agent is dodecyl mercaptan, mercaptoethanol, 3-mercaptopropanol, thioglycolic acid, mercaptomalic acid, isooctyl thioglycolate, n-butyl 3-mercaptopropionate or ethylene glycol dimercaptoacetate. alcohol esters.

The organic solvent is benzene, toluene, xylene, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, butyl acetate, propylene glycol, dipropylene glycol monomethyl ether or dipropylene glycol.

The mass ratio of macromonomer B to the total amount of small molecule A and macromonomer B is 0.1 to 80:100; the mass ratio of polymerization initiator-2 to the total amount of small molecule A and macromonomer B The ratio is 0.001 to 5:100; the molar ratio of chain transfer agent to polymerization initiator-2 is 0.1 to 10:1; the mass ratio of organic solvent to the total amount of macromonomer B and small molecule B is 0.5 to 5 :1.

In the suspension polymerization method, the following method is adopted: under the protection of nitrogen, the polymerization initiator-3, the chain transfer agent, the small molecular monomer A, and the macromolecular monomer B are mixed, and dispersed in the dissolved suspension stabilizer under mechanical stirring. agent and suspension stabilization aid in deionized water, and react at 40-80°C for 1-10 hours.

The mass ratio of macromonomer B to the total amount of small molecule A and macromonomer B is 0.1-80:100; the molar ratio of chain transfer agent to polymerization initiator-3 is 0.1-10:1; deionization The mass ratio of water to the total amount of small molecule monomer A and macromolecule B is 0.5 to 10:1; the mass ratio of suspension stabilizer to deionized water is 0.001 to 0.05:1; the mass ratio of suspension stabilizer to small molecule monomer The mass ratio of A to the total amount of macromonomer B is 0.001 to 0.05:1; the mass ratio of suspension stabilizer to suspension stabilization aid is 1 to 500:1; polymerization initiator-3 and small molecule A and macromonomer The mass ratio of the total amount of molecular monomer B is 0.001-5:100.

Described polymerization initiator-3 is all oil-soluble initiators.

The chain transfer agent is dodecyl mercaptan, mercaptoethanol, 3-mercaptopropanol, thioglycolic acid, mercaptomalic acid, isooctyl thioglycolate, n-butyl 3-mercaptopropionate or ethylene glycol dimercaptoacetate. alcohol esters.

The suspension stabilizer is one or both of organic suspending agent and inorganic suspending agent.

The suspension stabilization aid is sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium sulfate, sodium chloride, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, dodecylsulfonate One or more of sodium lauryl sulfate and sodium lauryl sulfate.

In emulsion polymerization, the following method is adopted: after the emulsifier is evenly dispersed in deionized water, then the mixed liquid of small molecular monomer A, macromonomer B and chain transfer agent is added, small molecular monomer A, macromolecular monomer The monomer B is emulsified in deionized water, and after nitrogen gas is passed through, the polymerization initiator-4 is added, and the reaction is carried out at 40-80° C. for 1-10 hours to obtain a comb-shaped graft copolymer.

The mass ratio of macromonomer B to the total amount of small molecule A and macromonomer B is 0.1-80:100; the mass ratio of emulsifier to deionized water is 0.001-0.05:1; polymerization initiator-4 The mass ratio of the total amount of the small molecular monomer A and the macromolecular monomer B is 0.001 to 5:100; the molar ratio of the chain transfer agent to the polymerization initiator-4 is 0.1 to 10:1; the emulsifier and the small molecular monomer The mass ratio of A to the total amount of macromonomer B is 0.001˜0.1:1.

Described polymerization initiator-4 is all water-soluble initiators.

The chain transfer agent is dodecyl mercaptan, mercaptoethanol, 3-mercaptopropanol, thioglycolic acid, mercaptomalic acid, isooctyl thioglycolate, n-butyl 3-mercaptopropionate or ethylene glycol dimercaptoacetate. alcohol esters.

The emulsifier is a cationic, anionic or nonionic emulsifier.

The preparation method of the macromonomer B is: using active hydrogen-containing mercaptan as a chain transfer agent, adopting free radical polymerization to polymerize (meth)acrylate monomers to obtain active hydrogen-containing oligomers; Then, the obtained oligomer is reacted with a (meth)acryloyl monomer that can react with active hydrogen in the presence of a catalyst and a polymerization inhibitor, and reacted at 0-100°C for 1-10 hours to obtain a macromolecule Monomer B.

The molar ratio of the active hydrogen-containing mercaptan to the (meth)acrylate monomer is 0.01-0.5:1, preferably 0.01-0.3:1; the molar ratio of the polymerization inhibitor to the active hydrogen-containing oligomer The ratio is 0.001 to 0.1:1; the molar ratio of the catalyst to the active hydrogen-containing oligomer is 0.001 to 0.1:1; The molar ratio is 0.3-1:1.

The (meth)acrylate monomer is a methacrylate monomer or an acrylate monomer; a methacrylate monomer is a monomer comprising a methacrylate unit in the molecule, and the acrylate A monomer is a monomer containing an acrylate unit in the molecule.

The mercaptan containing active hydrogen is an alkylene mercaptan or an aryl mercaptan containing an active hydrogen group, wherein the active hydrogen group in the aryl mercaptan containing active hydrogen can be a hydroxyl group or an amine group.

The (meth)acryloyl monomer that can react with active hydrogen is methacryloyl chloride, acryloyl chloride, methacrylate containing isocyanate or acrylate containing isocyanate.

The polymerization inhibitor is one or more of hydroquinone, cuprous chloride, phenothiazine, p-hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, preferably For phenothiazine or hydroquinone.

If the active hydrogen in the active hydrogen-containing oligomer is an amine group, and the (meth)acryl monomer reacting with it is methacrylate containing isocyanate or acrylate containing isocyanate, the catalyst used is dibutyltin Dilaurate or tertiary amine; if the active hydrogen in the active hydrogen-containing oligomer is a hydroxyl group, the (meth)acryloyl monomer reacting with it is methacrylate containing isocyanate or acrylate containing isocyanate, The catalyst used is dibutyltin dilaurate or tertiary amine; if the active hydrogen in the oligomer containing active hydrogen is a hydroxyl group, the (meth)acryloyl monomer reacting with it is methacryloyl chloride or acryloyl chloride , the catalyst used is a tertiary amine catalyst such as triethylamine;

The polymerization method described in the preparation process of macromonomer B is bulk polymerization or solution polymerization, preferably solution polymerization;

If the polymerization method adopts bulk polymerization in the preparation process of the oligomer containing active hydrogen, the specific steps are: under the protection of nitrogen, (meth)acrylate monomer, polymerization initiator-5 and sulfur containing active hydrogen Mix alcohols and react at 50-100°C for 1-10 hours to obtain oligomers containing active hydrogen; the molar ratio of mercaptans containing active hydrogen to (meth)acrylate monomers is 0.01-0.5:1, polymerized The mass ratio of the initiator-5 to the (meth)acrylate monomer is 0.01-5:100.

The polymerization initiator-5 is a water-soluble or oil-soluble polymerization initiator, the water-soluble initiator is all water-soluble initiators, and the oil-soluble initiator is all oil-soluble initiators.

If the polymerization method adopts solution polymerization in the preparation process of the oligomer containing active hydrogen, the specific steps are: under the protection of nitrogen, (meth)acrylate monomer, polymerization initiator-6 and sulfur containing active hydrogen Alcohol is dissolved in a solvent and reacted at 50-100°C for 1-10 hours to obtain an oligomer containing active hydrogen; the molar ratio of mercaptan containing active hydrogen to (meth)acrylate monomer is 0.01-0.5: 1. The mass ratio of polymerization initiator-6 to (meth)acrylate monomer is 0.01-5:100; the mass ratio of solvent to (meth)acrylate monomer is 0.1-10:1.

The solvent is an organic solvent or deionized water; wherein the organic solvent is benzene, toluene, xylene, tetrahydrofuran, methyl ethyl ketone, ethyl acetate or butyl acetate.

The polymerization initiator-6 is a water-soluble or oil-soluble polymerization initiator, the water-soluble initiator is all water-soluble initiators, and the oil-soluble initiator is all oil-soluble initiators.

Yet another object of the present invention is to provide an application of a reactive group-containing comb-shaped graft copolymer.

The comb-shaped graft copolymer of the present invention can be used as chain extender, compatibilizer, hydrolysis stabilizer, adhesive or anti-leakage agent of polymer or polymer blend, and is used for coating on wood, metal or plastic. layer.

The comb graft copolymers of the present invention can be used in extruders as additives to polymer blends. The comb graft copolymers according to the invention are especially suitable as chain extenders, compatibilizers and hydrolysis stabilizers in biodegradable polymers and polymer mixtures.

Comb graft copolymer of the present invention can add other additives such as fire retardant, surfactant, nucleating agent, coupling agent, filler, antioxidant, light stabilizer, compatibilizer, inorganic Fillers, colorants, antistatic agents, dyes, pigments, etc.

Beneficial effects of the present invention:

According to the present invention, can obtain a kind of comb-shaped graft copolymer that side chain contains reactive group, wherein reactive group and complementary group, as: amine group, carboxyl group and hydroxyl have very high reactivity, therefore can and End group reaction of various polyamides and polyesters. Methacrylate monomers and various polymers (such as polyvinylidene fluoride (PVDF), styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene terpolymer (ABS)) It is thermodynamically compatible. Thus, the synthesized reactive comb-graft copolymer can be used as a compatibilizer for many typical immiscible blend systems.

At the same time, because the reactive group can react with the terminal hydroxyl or carboxyl group of the polyester, the molecule can also be used as some polyester materials that are heat sensitive, easy to hydrolyze, have poor melt strength and insufficient mechanical properties, such as polylactic acid (PLA) , Polypropylene carbonate (PPC) chain extender, thereby improving the processing and application performance of the material.

The preparation process of the present invention is simple, and the molecular designability is strong. By rationally adjusting the length and type of the main chain and side chain in the molecule, the content of reactive groups and other parameters, an optimal ratio can be obtained, thereby achieving the most excellent compatibilization effect; It is easy to use and can be processed directly in the extruder.

Description of drawings

Fig. 1 is the infrared spectrogram of the reactive comb graft copolymer of gained in embodiment 2-2;

Fig. 2 is the stress-strain curve of the polylactic acid/polyvinylidene fluoride alloy in application example 3-1.

Detailed ways

The present invention is further analyzed below in conjunction with specific examples.

First for the preparation process of macromonomer B:

Example 1-1

Under a nitrogen atmosphere, 90 g of methyl methacrylate (0.9 mol), 10 g of glycidyl methacrylate (0.07 mol), 4 g of mercaptoethanol (0.05 mol), 2.5 g of 4,4' as polymerization initiator-6 - Azobis(4-cyanopentanol) and 100 g of tetrahydrofuran as a solvent were uniformly mixed, and the temperature of the reactor was raised to 70° C. for 5 hours. Then the reaction device was cooled to 0°C, 10g triethylamine (0.1mol), 8g methacryloyl chloride (0.08mol) were added to the reaction system, reacted at 0°C for 4 hours, and the solvent was removed under reduced pressure to obtain a large Molecular monomer B is denoted as M-2000 (E-0.1), the molecular weight of macromolecular monomer B is 2000, and the mass fraction of epoxy is 10%.

Example 1-2

Under a nitrogen atmosphere, 70 g methyl methacrylate (0.7 mol), 30 g glycidyl methacrylate (0.21 mol), 3.6 g mercaptoethanol (0.21 mol), 2.4 g of 4,4 as polymerization initiator-6 '-Azobis(4-cyanopentanol) and 100 g of tetrahydrofuran as a solvent were uniformly mixed, and the temperature of the reactor was raised to 70° C. for 5 hours. Then the reaction device was cooled to 0°C, 10g triethylamine (0.1mol) and 8g methacryloyl chloride (0.08mol) were added to the reaction system, reacted at 0°C for 4 hours, and then the solvent was removed under reduced pressure to obtain The macromonomer B is denoted as M-2000 (E-0.3), the molecular weight of the macromonomer B is 2000, and the mass fraction of epoxy is 30%.

Example 1-3

Under a nitrogen atmosphere, 40 g methyl methacrylate (0.4 mol), 60 g glycidyl methacrylate (0.42 mol), 3.2 g mercaptoethanol (0.04 mol), 1.9 g of 4,4 as polymerization initiator-6 '-Azobis(4-cyanopentanol) and 100 g of tetrahydrofuran as a solvent were uniformly mixed, and the temperature of the reactor was raised to 70° C. for 5 hours. Then the reaction device was cooled to 0°C, 10g triethylamine (0.1mol) and 8g methacryloyl chloride (0.08mol) were added to the reaction system, reacted at 0°C for 4 hours, and then the solvent was removed under reduced pressure to obtain The macromonomer B is denoted as M-2000 (E-0.6), the molecular weight of the macromonomer B is 2000, and the mass fraction of epoxy is 60%.

Example 1-4

In embodiment 1-2, the content of mercaptoethanol as chain transfer agent is replaced by 1.8 grams (0.02mol), and the content of triethylamine as catalyst is replaced by 4g (0.04mol), and methacryloyl chloride becomes 4.2g ( 0.04mol), other experimental conditions are consistent with embodiment 1-2, make macromolecular monomer B, denote as M-6000 (E-0.3), the molecular weight of macromolecular monomer B is 6000, and epoxy mass fraction is 30 %.

Example 1-5

The content of mercaptoethanol as chain transfer agent in embodiment 1-2 is replaced by 1.3 grams (0.017mol), the content of triethylamine as catalyst is replaced by 3g (0.03mol), and methacryloyl chloride becomes 3.1 g (0.029mol), other experimental conditions are consistent with embodiment 1-2, make macromolecular monomer B, denote as M-10000 (E-0.3), the molecular weight of macromolecular monomer B is 10000, epoxy mass fraction 30%.

Examples 1-6

Under a nitrogen atmosphere, 70 g methyl methacrylate (0.7 mol), 30 g glycidyl methacrylate (0.21 mol), 3.6 g mercaptoethanol (0.046 mol), 2.4 g of 4,4 as polymerization initiator-6 '-Azobis(4-cyanopentanol) and 100 g of tetrahydrofuran as a solvent were uniformly mixed, and the temperature of the reactor was raised to 70° C. for 5 hours. Then cool the reaction system to 50°C, add 0.04 g (6.3*10 ^-5 mol) of dibutyl dilaurate as a catalyst, and 0.06 g (5.5*10 ^-4 mol) of hydroquinone as a polymerization inhibitor , then slowly add 11 grams (0.071mol) of methacryloyloxyethyl isocyanate into the reaction system, react for 5 hours, remove the solvent under reduced pressure, and obtain macromonomer B with a molecular weight of 2000 and an epoxy mass fraction of 30 %.

Example 1-7

Under a nitrogen atmosphere, with 70g methyl methacrylate (0.7mol), 30g glycidyl methacrylate (0.21mol), 3.6g mercaptoethanol (0.046mol), 1.6g di-2 as polymerization initiator-6, 2'-Azabisisobutyronitrile and 100 g of tetrahydrofuran as a solvent were uniformly mixed, and the temperature of the reactor was raised to 70° C. for 5 hours. Then the reaction device was cooled to 0°C, 10g triethylamine (0.1mol), 8g methacryloyl chloride (0.08mol) were added to the reaction system, reacted at 0°C for 4 hours, and then the solvent was removed under reduced pressure to obtain Macromolecular monomer B, the molecular weight of macromolecular monomer B is 2000, and the mass fraction of epoxy is 30%.

Examples 1-8

Under nitrogen atmosphere, 50g methyl methacrylate (0.5mol), 20g ethyl acrylate (0.2mol), 30g glycidyl methacrylate (0.21mol), 3.6g mercaptoethanol (0.046mol), 2.4g as The 4,4'-azobis(4-cyanopentanol) of the polymerization initiator-6 and 100 g of tetrahydrofuran as a solvent were mixed evenly, and the temperature of the reactor was raised to 70° C. for 5 hours. Then the reaction device was cooled to 0°C, 10g triethylamine (0.1mol) and 8g methacryloyl chloride (0.08mol) were added to the reaction system, reacted at 0°C for 4 hours, and then the solvent was removed under reduced pressure to obtain Macromolecular monomer B, the molecular weight of macromolecular monomer B is 2000, and the mass fraction of epoxy is 30%.

Examples 1-9

Under nitrogen atmosphere, 50g methyl methacrylate (0.5mol), 20g ethyl acrylate (0.2mol), 30g glycidyl methacrylate (0.21mol), 3.6g mercaptoethanol (0.046mol), 2.4g as The 4,4'-azobis(4-cyanopentanol) of the polymerization initiator-6 and 100 g of tetrahydrofuran as a solvent were mixed evenly, and the temperature of the reactor was raised to 70° C. for 5 hours. Then the reaction device was cooled to 0°C, 10g triethylamine (0.1mol), 8g methacryloyl chloride (0.08mol) were added to the reaction system, reacted at 0°C for 4 hours, and then the solvent was removed under reduced pressure to obtain Macromolecular monomer B, the molecular weight of macromolecular monomer B is 2000, and the mass fraction of epoxy is 30%.

Utilize any macromonomer B that above-mentioned embodiment prepares to prepare the comb-shaped graft copolymer containing reactive group, embodiment is as follows:

The performance testing method of the comb-shaped graft copolymer containing reactive groups is as follows:

(1) Determination of the molecular weight of the comb-shaped graft copolymer containing reactive groups

The prepared comb-shaped graft copolymer was dissolved in chromatographically pure tetrahydrofuran at a concentration of 2 mg/ml, and the number-average molecular weight distribution was measured using gel permeation chromatography (GPC). Pure tetrahydrofuran.

Installation: Waters 515

Chromatographic column: two MZ-Gel SDplus 10.0μm packing diameter separation columns (10E5and )

Differential detector: Optilab T-rEX detector

Calibration curve: Narrow distribution polystyrene standard from 2000 to 10 ⁶ g*mol ^-1

(2) Determination of the molecular structure of the comb-shaped graft copolymer containing reactive groups

The molecular structure of the comb-shaped graft copolymer containing reactive groups was determined by Fourier transform infrared spectroscopy, and 910cm ^-1 was the characteristic peak of epoxy groups.

Device: Bruker, VERTEX 70V, scanning times 12 times, resolution 2cm ^-1

Embodiment 2-1～2-22 prepares comb-shaped graft copolymer for solution polymerization method:

Example 2-1

Under nitrogen protection, 100 grams of methyl methacrylate (MMA), 20 grams of the macromer B prepared in Example 1-1, 0.3 grams of 2,2'-azobisisobutyronitrile (AIBN) Add 0.2 gram of mercaptoethanol to 100 gram of toluene as a solvent, mix and mechanically stir for 30 minutes, raise the temperature of the reactor to 70° C. and react for 5 hours to obtain a comb-shaped graft copolymer containing reactive groups with a molecular weight of 22000 thing.

Embodiment 2-2～2-8

With reference to Example 2-1, according to the weight ratio change between macromonomer B and methyl methacrylate (MMA) in Table 1, the macromonomer is changed to the one prepared in embodiment 1-9 at the same time. Monomers and other experimental conditions were consistent with those in Example 2-1 to prepare reactive group-containing comb-shaped graft copolymers with different reactive group contents, different side chain lengths, and different side chain contents.

Each monomer composition ratio of Table 1 Embodiment 2-1～2-8

the monomer composition monomer weight ratio Example 2-1 M-2000(E-0.1)/MMA 2/8 Example 2-2 M-2000(E-0.3)/MMA 2/8 Example 2-3 M-2000(E-0.6)/MMA 2/8 Example 2-4 M-6000(E-0.3)/MMA 2/8 Example 2-5 M-10000(E-0.3)/MMA 2/8 Example 2-6 M-2000(E-0.1)/MMA 1/9 Example 2-7 M-2000(E-0.6)/MMA 5/5 Example 2-8 M-10000(E-0.3)/MMA 4/6

Example 2-9

In Example 2-1, 2,2'-azobisisobutyronitrile (AIBN) was replaced by dibenzoyl peroxide, mercaptoethanol was replaced by dodecylmercaptan, and other experimental conditions were the same as in Example 2- 1, a comb-shaped graft copolymer containing reactive groups was prepared.

Example 2-10

Under nitrogen protection, 2 grams of benzoyl peroxide, 1 gram of mercaptoacetic acid, 70 grams of macromonomer B prepared in Example 1-1, and 30 grams of p-methyl methacrylate were dissolved in 200 grams of methyl ethyl ketone, React at 70°C for 8 hours to prepare a comb-shaped graft copolymer containing reactive groups.

Embodiment 2-11～2-16

In Example 2-10, methyl ethyl ketone was replaced by ethyl acetate, butyl acetate, propylene glycol, dipropylene glycol monomethyl ether, and dipropylene glycol. Other experimental conditions were the same as in Example 2-10, and the reaction mixture containing group of comb-shaped graft copolymers.

Embodiment 2-17～2-21 prepares the comb-shaped graft copolymer containing reactive group for suspension polymerization method:

Example 2-17

Mix 0.3 grams of 2,2'-azobisisobutyronitrile (AIBN), 0.1 grams of 3-mercaptopropanol, 70 grams of methyl methacrylate, and 30 grams of the macromer B prepared in Example 1-1 Uniformly, a monomer mixture is obtained. 1.5 g of sodium dihydrogen phosphate was dissolved in 300 g of deionized water while 2 g of polyvinylpyrrolidone was added thereto. Add the monomer mixture into the above solution, stir mechanically evenly, and purge the reactor with nitrogen at the same time. After the reaction was carried out at 65°C for 4 hours, the reaction product was suction filtered, washed with water and dried to obtain a comb-shaped graft copolymer containing reactive groups with a number average molecular weight of 24,000.

Example 2-18

Under nitrogen protection, 60 grams of macromonomer B prepared in Example 1-1, 40 grams of macromonomer B prepared in Example 1 and 0.1 gram of isooctyl thioglycolate were mixed. 1 g of sodium monohydrogen phosphate was dissolved in 1000 g of deionized water while 2 g of polyvinyl alcohol was added thereto. Add the monomer mixture to the above solution, stir it evenly, and purge the reactor with nitrogen, then add 0.01 g of K ₂ S ₂ O ₈ -FeSO ₄ , react at 40°C for 10 hours, filter the reaction product with water, wash with water and Drying and dehydration obtains a comb-shaped graft copolymer containing reactive groups.

Example 2-19

Under nitrogen protection, 50 grams of macromonomer B prepared in Example 1-1, 50 grams of butyl methacrylate and 0.2 grams of ethylene glycol dimercaptoacetate were mixed uniformly. Dissolve 0.1 g of sodium lauryl sulfate and 2 g of gelatin in 300 g of deionized water. Add the monomer mixture to the above solution, stir mechanically evenly, and purge the reactor with nitrogen, then add 2 grams of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and react at 80°C After 1 hour, the reaction product was suction-filtered, washed with water, dried and dehydrated to obtain a comb-shaped graft copolymer containing reactive groups.

Example 2-20

Under nitrogen protection, 0.3 g of 2,2'-azobisisobutyronitrile (AIBN), 40 g of macromonomer B prepared in Example 1-1, 60 g of methyl methacrylate and 1 g of 3- n-Butyl mercaptopropionate mixed evenly. 2 g of basic calcium phosphate and 0.03 g of sodium dodecylbenzenesulfonate were dissolved in 200 g of deionized water. Add the monomer mixture into the above solution, mechanically stir it evenly, and at the same time, purge the reactor with nitrogen, react at 60°C for 5 hours, filter the reaction product with suction, wash with water and dry and dehydrate to obtain a comb-shaped graft copolymer containing reactive groups .

Example 2-21

Under nitrogen protection, 0.1 gram of 2,2'-azobisisobutyronitrile (AIBN), 1 gram of isooctyl mercaptoacetate, 20 grams of macromonomer B prepared in Example 1-1, 80 grams of methyl Methyl acrylate and mix well. Dissolve 1 g of hydroxypropyl methylcellulose and 0.01 g of cetyltrimethylammonium bromide in 100 g of deionized water. Add the monomer mixture into the above solution, mechanically stir it evenly, and at the same time, purge the reactor with nitrogen, react at 60°C for 5 hours, filter the reaction product with suction, wash with water and dry and dehydrate to obtain a comb-shaped graft copolymer containing reactive groups .

Embodiment 2-22～embodiment 2-24 adopts emulsion polymerization method to prepare the comb-shaped graft copolymer containing reactive group:

Example 2-22

Under the protection of nitrogen, 0.4 gram of emulsifier TWEEN-80 and 200 gram of deionized water were sequentially added to the reaction device, then 90 gram of methyl methacrylate, 10 gram of macromonomer B prepared in Example 1-1 and 0.3 g of mercaptomalic acid mixture was added to the reactor for emulsification, and finally 0.2 g of K ₂ S ₂ O ₈ -FeSO ₄ was added, and the reaction was carried out at 65°C for 4 hours to obtain a comb containing reactive groups with a number average molecular weight of 23,000. shaped graft copolymers.

Example 2-23

Under the protection of nitrogen, 2 grams of dodecyltrimethylammonium bromide were uniformly dispersed in 1 kilogram of deionized water, and then 80 grams of methyl methacrylate and 20 grams of the macromolecular unit prepared in Example 1-1 were added. The mixture of body B and 0.2 g of mercaptomalic acid was emulsified in deionized water, and after passing through nitrogen gas, 0.2 g of K ₂ S ₂ O ₈ -FeSO ₄ was added and reacted at 40°C for 10 hours to obtain a comb-shaped compound containing reactive groups. graft copolymer.

Example 2-24

Under the protection of nitrogen, 10 grams of sodium lauryl sulfate was evenly dispersed in 300 grams of deionized water, and then 20 grams of macromer B prepared in Example 1-1, 80 grams of methyl methacrylate and A mixture of 0.5 g of mercaptoethanol was emulsified in deionized water, and finally 5 g of 2,2'-azobisisobutylamidine dihydrochloride was reacted at 80°C for 1 hour to obtain a comb-shaped junction containing reactive groups. branch copolymers.

Embodiment 2-25～2-26 prepares the comb-shaped graft copolymer containing reactive group for bulk polymerization:

Example 2-25

Under nitrogen protection, mix 0.001 g of 2,2'-azobisisobutyronitrile (AIBN), 0.003 g of mercaptoethanol, 0.1 g of macromer B, and 99.9 g of methyl methacrylate, and react at 50°C for 3 Hours, a comb-shaped graft copolymer containing reactive groups was obtained.

Example 2-26

Under nitrogen protection, 0.001 gram of 2,2'-azobisisobutyronitrile (AIBN), 0.002 gram of dodecyl mercaptan, 40 gram of macromer B prepared in Example 1-1, 10 gram Ethyl acrylate and 50 g of methyl methacrylate were uniformly mixed and reacted at 90° C. for 1 hour to obtain a comb-shaped graft copolymer containing reactive groups.

Fig. 1 is the infrared spectrogram of the reactive comb graft copolymer of gained in embodiment 2-2;

The position at 910 cm ^-1 is the characteristic vibration peak of the epoxy group, which proves that the side chain of the reactive comb-shaped graft copolymer contains epoxy groups.

The following is the preparation of polylactic acid/polyvinylidene fluoride (PLLA/PVDF) alloy:

The stress-strain curve of polylactic acid/polyvinylidene fluoride (PLLA/PVDF) alloy was tested according to JIS-K7113 standard, and the tensile machine model was Instron 5966.

Application Example 3-1:

The reactive group-containing comb-shaped graft copolymer of the present invention in embodiment 2-2, PLLA, PVDF are added in the internal mixer (HAAKE Polylab QC) according to the ratio of Table 2 and mixed, and mixed for 10 minutes at 190 degrees Celsius , the rotor speed is 50 rpm.

Application Example 3-2:

As shown in Table 2, other conditions are according to the application example 3-1, the PVDF feeding amount is changed to 35 grams, and the PLLA is changed to 15 grams.

Application Example 3-3:

As shown in Table 2, the other conditions are according to the application example 3-1, the PVDF feeding amount is changed to 15 grams, and the PLLA is changed to 35 grams.

Formulation and material property table of table 2 application examples 1～3

Comparative example: as shown in Table 3, other conditions are as in Application Example 3-1, but no reactive group-containing graft copolymer of the present invention is added.

Formulation and material property table of table 3 comparative example

Show in table 2, 3, after adding 3wt% graft copolymer of the present invention relative to PLLA and PVDF gross mass as compatibilizer, can significantly improve the elongation at break of PLLA/PVDF alloy, illustrate that the present invention comb-shaped graft Copolymer is an efficient compatibilizer.

Fig. 2 is the stress-strain curve of the polylactic acid/polyvinylidene fluoride alloy in application example 3-1.

This proves that the addition of the reactive comb molecules greatly improves the mechanical properties of the polylactic acid/polyvinylidene fluoride alloy material.

The above embodiments do not limit the present invention, and the present invention is not limited to the above embodiments, as long as the requirements of the present invention are met, they all belong to the protection scope of the present invention.

Claims (10)

1., containing the comb-shaped graft copolymer of reactive group, it is characterized in that the comb-shaped graft copolymer that this multipolymer be main chain is small molecule monomer A, side chain is macromonomer B; The weight of macromonomer B is 0.1wt ﹪ ~ 80wt ﹪ of comb-shaped graft copolymer quality, and the weight of small molecule monomer A is 99.9wt ﹪ ~ 20wt ﹪ of comb-shaped graft copolymer quality;

The number-average molecular weight of described comb-shaped graft copolymer is 5000 ~ 100000;

Described macromonomer B general formula (1) represents:

Wherein R ₁, R ₂for hydrogen atom or methyl, R ₃for methyl, ethyl, butyl, the tertiary butyl or glycidyl, R ₄for hydrogen atom or sec-butyl, X represents-CH ₂cH (OH) CH ₂-or-Z-NHCO-, Y be-L ₁-L ₂-S-, Z are-(CH ₂cH ₂o) _a(CH ₂) _b-, L ₁for Direct Bonding ,-O-,-COO-or-NH-, L ₂for C1 ~ C20 alkylidene group or C6 ~ C20 aryl, S represents sulphur atom, and n is the integer of 5 ~ 100, m be 0 or 1, a be the integer of 0 ~ 20, b is the integer of 1 ~ 20;

The number-average molecular weight of described macromonomer B is 500 ~ 10000;

Described small molecule monomer A is one or more of methacrylic ester, acrylate, hydroxyl ester, Methacrylamide, unsaturated nitrile, styrene monomer and derivative thereof.

2. a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 1, is characterized in that the weight of small molecule monomer A is 80wt ﹪ ~ 50wt ﹪ of comb-shaped graft copolymer quality; The weight of macromonomer B is 5wt ﹪ ~ 50wt ﹪ of comb-shaped graft copolymer quality; The number-average molecular weight of comb-shaped graft copolymer is 15000 ~ 60000.

3. preparation a kind of method containing the comb-shaped graft copolymer of reactive group as claimed in claim 1, is characterized in that the method is that small molecule monomer A and macromonomer B copolymerization are formed the comb-shaped graft copolymer that main chain is small molecule monomer A, side chain is macromonomer B; The add-on of macromonomer B is 0.1wt ﹪ ~ 80wt ﹪ of comb-shaped graft copolymer quality, and the add-on of small molecule monomer A is 99.9wt ﹪ ~ 20wt ﹪ of comb-shaped graft copolymer quality;

The number-average molecular weight of described comb-shaped graft copolymer is 5000 ~ 100000;

Described small molecule monomer A is one or more of methacrylic ester, acrylate, hydroxyl ester, Methacrylamide, unsaturated nitrile, styrene monomer and derivative thereof.

4. the preparation method of a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterized in that described copolymerization process is mass polymerization, concrete operations are under nitrogen protection, polymerization starter-1, chain-transfer agent, small molecule monomer A, macromonomer B are mixed, react 1 ~ 10 hour at 50 ~ 120 DEG C, obtain comb-shaped graft copolymer;

Described polymerization starter-1 is oil-soluble initiator;

Described chain-transfer agent is lauryl mercaptan, mercaptoethanol, 3-mercaprol, Thiovanic acid, Thiomalic acid, isooctyl mercaptoacetate, the positive butyl ester of 3-thiohydracrylic acid or glycol dimercaptosuccinate;

The mass ratio of macromonomer B and small molecule monomer A and macromonomer B total amount is 0.1 ~ 80:100; Oil polymerization starter-1 is 0.001 ~ 5:100 with the mass ratio of small molecule monomer A and macromonomer B total amount; The mol ratio of chain-transfer agent and polymerization starter-1 is 0.1 ~ 10:1.

5. the preparation method of a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterized in that described copolymerization process is solution polymerization process, concrete operations are under nitrogen protection, polymerization starter-2, chain-transfer agent, small molecule monomer A, macromonomer B are dissolved in organic solvent, react 1 ~ 10 hour at 50 ~ 120 DEG C;

Described polymerization starter-2 is water-soluble or oil-soluble initiator;

Described chain-transfer agent is lauryl mercaptan, mercaptoethanol, 3-mercaprol, Thiovanic acid, Thiomalic acid, isooctyl mercaptoacetate, the positive butyl ester of 3-thiohydracrylic acid or glycol dimercaptosuccinate;

Described organic solvent is benzene,toluene,xylene, tetrahydrofuran (THF), methylethylketone, ethyl acetate, butylacetate, propylene glycol, dipropylene glycol methyl ether or dipropylene glycol;

The mass ratio of macromonomer B and small molecule monomer A and macromonomer B total amount is 0.1 ~ 80:100; Polymerization starter-2 is 0.001 ~ 5:100 with the mass ratio of small molecule monomer A and macromonomer B total amount; The mol ratio of chain-transfer agent and polymerization starter-2 is 0.1 ~ 10:1; The mass ratio of organic solvent and macromonomer B and small molecule monomer B total amount is 0.5 ~ 5:1.

6. the preparation method of a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterized in that described copolymerization process is suspension polymerization, concrete operations are under nitrogen protection, polymerization starter-3, chain-transfer agent, small molecule monomer A, macromonomer B are mixed, be scattered in the deionized water being dissolved with suspension stabilizer and suspension stabilization aid under mechanical stirring, react 1 ~ 10 hour at 40 ~ 80 DEG C;

The mass ratio of macromonomer B and small molecule monomer A and macromonomer B total amount is 0.1 ~ 80:100; The mol ratio of chain-transfer agent and polymerization starter-3 is 0.1 ~ 10:1; The mass ratio of deionized water and small molecule monomer A and macromonomer B total amount is 0.5 ~ 10:1; The mass ratio of suspension stabilizer and deionized water is 0.001 ~ 0.05:1; The mass ratio of suspension stabilizer and small molecule monomer A and macromonomer B total amount is 0.001 ~ 0.05:1; The mass ratio of suspension stabilizer and suspension stabilization aid is 1 ~ 500:1; Polymerization starter-3 is 0.001 ~ 5:100 with the mass ratio of small molecule monomer A and macromonomer B total amount;

Described polymerization starter-3 is oil-soluble initiator;

Described chain-transfer agent is lauryl mercaptan, mercaptoethanol, 3-mercaprol, Thiovanic acid, Thiomalic acid, isooctyl mercaptoacetate, the positive butyl ester of 3-thiohydracrylic acid or glycol dimercaptosuccinate;

Described suspension stabilizer be organic suspending agent, Inorganic suspending agent one or both;

Described suspension stabilization aid is one or more in disodium-hydrogen, SODIUM PHOSPHATE, MONOBASIC, sodium sulfate, sodium-chlor, cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate.

7. the preparation method of a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterized in that described copolymerization process is letex polymerization, concrete operations are after emulsifying agent is dispersed in deionized water, then the mixed solution of small molecule monomer A, macromonomer B and chain-transfer agent is added, small molecule monomer A, macromonomer B emulsification in deionized water, react 1 ~ 10 hour at adding polymerization starter-4,40 ~ 80 DEG C after passing into nitrogen, obtain comb-shaped graft copolymer;

The mass ratio of macromonomer B and small molecule monomer A and macromonomer B total amount is 0.1 ~ 80:100; The mass ratio of emulsifying agent and deionized water is 0.001 ~ 0.05:1; Polymerization starter-4 is 0.001 ~ 5:100 with the mass ratio of small molecule monomer A and macromonomer B total amount; The mol ratio of chain-transfer agent and polymerization starter-4 is 0.1 ~ 10:1; The mass ratio of emulsifying agent and small molecule monomer A and macromonomer B total amount is 0.001 ~ 0.1:1;

Described polymerization starter-4 is water soluble starter;

Described chain-transfer agent is lauryl mercaptan, mercaptoethanol, 3-mercaprol, Thiovanic acid, Thiomalic acid, isooctyl mercaptoacetate, the positive butyl ester of 3-thiohydracrylic acid or glycol dimercaptosuccinate;

Described emulsifying agent is the emulsifying agent of cationic, anionic or non-ionic type.

8. the preparation method of a kind of comb-shaped graft copolymer containing reactive group as described in claim 3 or 4 or 5 or 6 or 7, it is characterized in that the preparation method of described macromonomer B is: using the mercaptan containing active hydrogen as chain-transfer agent, adopt Raolical polymerizable polymerization (methyl) acrylic ester monomer, obtain the oligopolymer containing active hydrogen; Then by the oligopolymer that obtains under catalyzer and stopper existent condition, with containing can and (methyl) acryloyl monomer of reactive with active hydrogen react, at 0 ~ 100 DEG C, reaction 1 ~ 10 hour, obtains macromonomer B;

Described is 0.01 ~ 0.5:1 containing the mercaptan of active hydrogen and the mol ratio of (methyl) acrylic ester monomer; Stopper is 0.001 ~ 0.1:1 with the mol ratio of the oligopolymer containing active hydrogen; Catalyzer is 0.001 ~ 0.1:1 with the mol ratio of the oligopolymer containing active hydrogen; Mol ratio containing the oligopolymer of active hydrogen and (methyl) acryloyl monomer of energy and reactive with active hydrogen is 0.3 ~ 1:1;

Described (methyl) acrylic ester monomer is methacrylate ester monomer or acrylic ester monomer; Methacrylate ester monomer is the monomer comprising methacrylate unit in molecule, and acrylic ester monomer is the monomer comprising acrylic ester unit in molecule;

The described mercaptan containing active hydrogen is alkylidene group mercaptan or the aryl mercaptan containing active hydrogen base, wherein can be hydroxyl or amido containing active hydrogen group in the aryl mercaptan of active hydrogen;

Described (methyl) acryloyl monomer containing energy and reactive with active hydrogen is methacrylic chloride, acrylate chloride, the methacrylic ester containing isocyanic ester or the acrylate containing isocyanic ester;

Described stopper is one or more in Resorcinol, cuprous chloride, thiodiphenylamine, MEHQ, 2,6 di tert butyl 4 methyl phenol;

If be amido containing the active hydrogen in the oligopolymer of active hydrogen, (methyl) acryloyl monomer reacted with it is the methacrylic ester containing isocyanic ester or the acrylate containing isocyanic ester, then the catalyzer used is dibutyltin dilaurate or tertiary amine; If be hydroxyl containing the active hydrogen in the oligopolymer of active hydrogen, (methyl) acryloyl monomer reacted with it is the methacrylic ester containing isocyanic ester or the acrylate containing isocyanic ester, then the catalyzer used is dibutyltin dilaurate or tertiary amine; If be hydroxyl containing the active hydrogen in the oligopolymer of active hydrogen, (methyl) acryloyl monomer reacted with it is methacrylic chloride or acrylate chloride, and the catalyzer of use is the tertiary amine catalysts such as triethylamine.

9. the preparation method of a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 8, is characterized in that described is 0.01 ~ 0.3:1 containing the mercaptan of active hydrogen with the mol ratio of (methyl) acrylic ester monomer; Described stopper is thiodiphenylamine or Resorcinol.

10. a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 1, it is characterized in that this multipolymer can be used as the chainextender of polymkeric substance or blend polymer, expanding material, hydrolysis stabilizer, tackiness agent or sealant, the coating on timber, metal or plastics.