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CN108239241B - Graft copolymer containing isocyanate group and application thereof - Google Patents

Graft copolymer containing isocyanate group and application thereof Download PDF

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CN108239241B
CN108239241B CN201611226763.3A CN201611226763A CN108239241B CN 108239241 B CN108239241 B CN 108239241B CN 201611226763 A CN201611226763 A CN 201611226763A CN 108239241 B CN108239241 B CN 108239241B
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graft copolymer
carbon
polymer
monomer
carbon double
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CN108239241A (en
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李坤泉
柴生勇
刘振峰
李积德
孔蕾
陈林
刘勤
李岩
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Kingfa Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C08F212/08—Styrene
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
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    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/48—Acrylonitrile with nitrogen-containing monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F

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Abstract

The invention discloses a graft copolymer containing isocyanate groups and application thereof. The graft copolymer is a polymer containing isocyanate groups and a high molecular copolymer side chain, and is mainly prepared by copolymerizing 40-90 wt% of monomer A containing carbon-carbon double bonds, 5-30 wt% of unsaturated monomer B containing isocyanate groups and 5-30 wt% of high molecular polymer C containing carbon-carbon double bonds through free radical polymerization. The preparation process comprises the following steps: firstly, obtaining a high molecular polymer D by utilizing free radical copolymerization, and then preparing a high molecular polymer C containing carbon-carbon double bonds by utilizing the reaction among groups; and finally, carrying out free radical copolymerization on the obtained high molecular polymer C, the monomer A and the monomer B, and drying and devolatilizing to obtain the graft copolymer containing the isocyanate groups. The graft copolymer containing isocyanate groups can be used as a compatibilizer of a polymer blend and a chain extender of the polymer.

Description

Graft copolymer containing isocyanate group and application thereof
Technical Field
The invention relates to the field of synthesis and application of graft copolymers, in particular to an acrylate graft copolymer containing isocyanate groups and application thereof.
Background
The compatibilizer is an assistant which promotes incompatible blending systems to be combined together by physical or chemical means so as to obtain a stable blending system. For polymer blends, phase separation occurs due to differences in chemical structure, polarity, molecular weight (viscosity), and crystallinity between the components, resulting in poor polymer blend properties. Therefore, the compatibilizer is a cornerstone of a high-level blending modified product. Particularly, in the current markets of raw materials and modified materials, the production formula and the process flow of enterprises are mostly disclosed and transparent, and the addition of the compatibilizer becomes the key point of differentiation between material modification manufacturers and competitors.
For polymer blends containing reactive groups in the system, reactive compatibilizers are often used. Most of the common reactive compatibilizers are graft polymers, such as PP grafted maleic anhydride (Chinese patent CN 102924661B, CN 101519477B), styrene grafted maleic anhydride (Chinese patent CN 102993350B), ABS grafted maleic anhydride, and the like. The compatibilizer is prepared by grafting functional groups on a polymer molecular chain by adopting a melt reaction extrusion method, so that the grafting reaction type compatibilizer is obtained, and the production process is simple. Although the compatibilizer can solve the problem of the compatibility of the blended polymer alloy to a certain extent, the compatibilizer has the advantages of single variety, low grafting rate, more side reactions and difficult control of the reaction due to process limitation. In actual use, the addition amount is large, and the compatibilization efficiency is low, so that the compatibilizer obtained by the melt grafting method cannot meet the actual requirement.
In order to realize effective control on the structure and grafting ratio of the compatibilizer, DuPont uses a copolymerization method to prepare an ethylene-butyl acrylate-glycidyl methacrylate (PTW) terpolymer compatibilizer as early as the invention patent US3723570 of 1973. On the basis, Chinese patent CN 101851321B adopts a suspension polymerization process to prepare a terpolymer compatibilizer styrene-acrylonitrile-glycidyl methacrylate (SAG) compatibilizer, the content of epoxy groups can be controlled by the method, a compatibilizer product with high grafting rate can be obtained, and the grafting rate of epoxy can be up to 10%. The system contains styrene and acrylonitrile units, so the compatibilizer is particularly suitable for ABS alloy systems. Compared with other compatibilizers, the compatibilizer can effectively improve the compatibility (CN 102181122A) of ABS and polyethylene terephthalate (PET) alloy and the thermal stability (CN 104877326A) of polycarbonate and ABS alloy.
The structure of the compatibilizer is mostly a linear copolymer compatibilizer, and in practical application, the content of the reactive group with high grafting rate can improve the compatibility with one phase, but the reactive group and the other phase state can only depend on the winding among molecular chains, so that the acting force is weak. By adjusting the structure of the compatibilizer, the grafting rate of the reactive groups is ensured, and meanwhile, a high polymer chain segment which is thermodynamically compatible with another phase state is introduced into the main chain, so that the winding between the high polymer chains and the compatibility between two phases can be effectively improved. Chinese patent CN 103421154A discloses a comb-type graft copolymer containing reactive groups, and a preparation method and application thereof. The patent obtains a comb polymer with high grafting rate by introducing polyacrylate homopolymer chain segments on polymer side chains and adopting a free radical copolymerization method. Compared with the commercial Compatibilizer, the Compatibilizer can effectively improve the modulus, elongation at break, yield strength, tensile strength and the like of PET/ABS alloy, and has higher compatibilization efficiency than a linear Compatibilizer with the same grafting ratio (WY Dong, HT Wang, MF He, et al. Synthesis of Reactive Comb Polymers and graft Polymers as a high effective compatibility in an inert polymeric blends [ J ]. Industrial & Engineering Chemistry Research, 2015, 54: 2081-. The comb-type graft copolymer obtained by the invention patent also has the function of chain extension. However, the polymer chain segment of the side chain of the compatibilizer in the patent is mainly a homopolymer of a methacrylate or acrylate monomer, and the side chain and another phase state are not well compatible in practical application. Meanwhile, the single homopolymer on the side chain of the compatibilizer has specific polarity and solubility parameters, and the application of the compatibilizer is limited to a certain extent.
Disclosure of Invention
The invention aims to provide a novel high-efficiency graft copolymer containing isocyanate groups, aiming at overcoming the defects of the existing polymer blend compatibilization technology.
The invention also aims to provide the application of the graft copolymer containing the isocyanate group as a polymer blend compatibilizer and a polymer chain extender.
The purpose of the invention is realized by the following technical scheme:
a graft copolymer containing isocyanate groups, wherein the graft copolymer is a polymer containing isocyanate groups and macromolecular copolymer side chains and is prepared by the reaction of the following substances:
40-90 wt% of monomer A containing carbon-carbon double bond;
5-30 wt% of unsaturated monomer B containing isocyanate group;
5-30 wt% of a high molecular polymer C containing carbon-carbon double bonds;
the number average molecular weight of the graft copolymer containing isocyanate groups is 11000-73000, and the weight average molecular weight is 36000-144000.
The invention utilizes the reaction of a high molecular polymer C containing carbon-carbon double bonds, a monomer A containing carbon-carbon double bonds and an unsaturated monomer B containing isocyanate groups to obtain the graft copolymer containing the isocyanate groups. When the carbon-carbon double bond grafted copolymer is used as a compatibilizer, the compatibility of an isocyanate group and one phase can be improved, the high molecular polymer C containing carbon-carbon double bonds is used as a side chain of the grafted copolymer, the copolymer is introduced, the flexibility of the molecular chain of the side chain can be controlled by adjusting the selection and the proportion of different monomers, the solubility parameter of the polymer chain segment of the side chain can be adjusted, the compatibility of the compatibilizer and the other phase can be better improved, and the binding force between the two phases can be enhanced. Compared with the linear and comb-shaped structure compatibilizers obtained in the prior art, the graft copolymer containing isocyanate groups prepared by the invention has better compatibilization effect under the condition of similar molecular weight, and can be used as a compatibilizer and a polymer chain extender of a polymer blend alloy.
The graft copolymer containing isocyanate groups is prepared by the following reaction:
60-85 wt% of monomer A containing carbon-carbon double bond;
5-20 wt% of unsaturated monomer B containing isocyanate group;
10-20 wt% of a high molecular polymer C containing carbon-carbon double bonds.
The high molecular polymer C containing the carbon-carbon double bond is obtained by reacting a polymer D with a monomer E containing the carbon-carbon double bond, wherein the chemical general formula of the polymer D is as follows:
Figure DEST_PATH_IMAGE002
wherein R is1Is methyl, ethyl or butyl, R2Is a hydrogen atom or a methyl group, R3Is methyl, ethyl, propyl, butyl, tert-butyl or octyl when R is2When it is methyl, R1、R3Different; m is an integer of 20-100, k is an integer of 1-99, n is an integer of 1-100, and q is an integer of 2-12; s is sulfur atom, G is a group which reacts with the monomer E containing carbon-carbon double bond, and is one of carboxyl, amino or hydroxyl.
Preferably, the number average molecular weight of the high molecular polymer C containing the carbon-carbon double bond is 4000-12000.
The glass transition temperature of the high molecular polymer C containing the carbon-carbon double bond is 10-100 ℃.
The monomer E containing carbon-carbon double bonds is provided with epoxy groups, amino groups, isocyanate groups or acyl chloride groups.
Preferably, the monomer E containing carbon-carbon double bonds is one of acrylamide or methacrylamide, glycidyl methacrylate or allyl glycidyl ether, acryloyl chloride or methacryloyl chloride, methacryloyloxyethyl isocyanate and derivatives thereof.
The molar ratio of the polymer D to the monomer E containing the carbon-carbon double bond is 1: 0.8-1.3.
The monomer A containing carbon-carbon double bonds is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, styrene, α -methyl styrene, α -ethyl styrene, acrylonitrile, methacrylonitrile and derivatives thereof.
The unsaturated monomer B containing isocyanate groups is one or more of isocyano ethyl methacrylate, 3-isopropyl-dimethyl benzyl isocyanate, isocyanate ethyl acrylate and derivatives thereof.
The polymer D is prepared by the free radical polymerization initiated by one or more of acrylate or methacrylate monomers and a chain transfer agent through an initiator; the chain transfer agent is one of aliphatic mercaptan containing carboxyl, hydroxyl or amino; the initiator is one of azo initiator, peroxide initiator or redox initiator.
The graft copolymer containing isocyanate groups is prepared by copolymerizing a monomer A containing carbon-carbon double bonds, an unsaturated monomer B containing isocyanate groups and a high molecular polymer C containing carbon-carbon double bonds by a free radical polymerization method.
The free radical polymerization method is solution polymerization.
The viscous state temperature of the graft copolymer containing isocyanate groups is 110-200 ℃.
Preferably, the viscosity state temperature of the graft copolymer containing isocyanate groups is 140 ℃ to 180 ℃.
The graft copolymer containing isocyanate groups can be granules made by a granulator and a granulator; or the powder made by a pulverizer.
The graft copolymer containing isocyanate groups can be used as a compatibilizer of a polymer blend and a chain extender of a polymer.
Compared with the prior art, the invention has the following beneficial effects:
the graft copolymer containing isocyanate groups prepared by the invention is used as a compatibilizer, the compatibility of the graft copolymer with one phase can be improved by high-content isocyanate groups, the flexibility of the molecular chain of the side chain can be controlled by the copolymer of polyacrylate introduced into the side chain through the selection and the proportion of different acrylate monomers, the solubility parameter of the polymer chain segment of the side chain can be adjusted, the compatibility of the graft copolymer with the other phase can be better improved, and the binding force between the two phases can be enhanced. The graft copolymer containing isocyanate groups prepared by the invention can also generate a crosslinking reaction with a polymer, so that the molecular weight of the polymer is improved, and the graft copolymer plays a role of a chain extender; compared with the common linear polymer chain extender, the graft copolymer obtained by the invention has higher molecular weight and more obvious chain extension effect.
Drawings
FIG. 1 is a GPC chart of the isocyanate group-containing graft copolymer prepared in example 1.
Detailed Description
The present invention is further explained with reference to specific embodiments, which are described in detail and specific, but not to be construed as limiting the scope of the invention, the technical solutions obtained by equivalents or equivalent changes should be included in the scope of the claims of the present invention.
In the following examples, all the raw materials used were commercially available products.
Testing and characterizing method
(one) Gel Permeation Chromatography (GPC) assay
Dissolving the obtained graft copolymer containing isocyanate groups by using tetrahydrofuran, determining the retention time of the polymer by using a gel permeation chromatograph, wherein a detection instrument is a refractive index determinator, a mobile phase is tetrahydrofuran, and monodisperse polystyrene is used as a standard sample to calculate the relative molecular weight and the distribution of the polymer.
(II) measurement of temperature in viscous state
Heating and melting the obtained graft copolymer containing the isocyanate groups, preparing a sheet with the thickness of about 2mm, testing the temperature-deformation curve of the copolymer by using a thermomechanical analyzer (TMA), and obtaining the viscous state temperature of the copolymer according to the temperature-deformation curve.
Example 1
Under the protection of nitrogen, 80g of methyl methacrylate, 20g of ethyl acrylate, 1.5g of chain transfer agent mercaptopropanol, 4.5g of initiator azobisisobutyronitrile and 200g of solvent toluene are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 65 ℃, and after reaction for 6 hours, a toluene solution containing polymer D is obtained; cooling the reaction system to room temperature, adding 0.01g of hydroquinone serving as a polymerization inhibitor, 0.04g of N, N-dimethylbenzylamine serving as a catalyst and 2.1g of monomer E methacryloyl chloride containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 1.2), stirring at room temperature for reaction for 8 hours, evaporating the product to dryness in a rotary manner to obtain a high-molecular polymer C containing carbon-carbon double bonds, wherein the number average molecular weight of the obtained high-molecular polymer C is about 4200 according to GPC (gel permeation chromatography) tests.
Under the protection of nitrogen, 80g of methyl methacrylate, 40g of butyl acrylate, 20g of isocyanoethyl methacrylate, 10g of the prepared high molecular polymer C containing carbon-carbon double bonds, 4.5g of azobisisobutyronitrile and 210g of xylene are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are respectively 80.00wt%, 13.33wt% and 6.67 wt%), the mixture is moved into a four-neck flask provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 75 ℃, the reaction is carried out for 6 hours, and the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. Through GPC measurement, as can be seen from FIG. 1, the obtained isocyanate group-containing graft copolymer had a number average molecular weight of about 14746 and a weight average molecular weight of 47114; the resulting isocyanate group-containing graft copolymer had a viscous state temperature of about 153 ℃.
Example 2
Under the protection of nitrogen, 60g of methyl methacrylate, 50g of butyl acrylate, 1.5g of chain transfer agent mercaptopropanol, 3.5g of initiator azobisisobutyronitrile and 250g of solvent ethyl acetate are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 65 ℃, and after reaction for 6 hours, an ethyl acetate solution containing polymer D is obtained; cooling the reaction system to room temperature, adding 0.01g of hydroquinone serving as a polymerization inhibitor, 0.02g of triethylamine serving as a catalyst and 2.1g of monomer E methacryloyl chloride containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 1.2), stirring at room temperature for reaction for 5 hours, and then drying the product by rotary evaporation to obtain the high-molecular polymer C containing the carbon-carbon double bonds. The number average molecular weight of the resulting high molecular polymer C was found to be about 5310 by GPC measurement.
Under the protection of nitrogen, 100g of styrene, 30g of ethyl acrylate, 20g of isocyanate ethyl acrylate, 50g of the prepared high molecular polymer C containing carbon-carbon double bonds, 2.1g of azobisisobutyronitrile and 300g of butyl acetate are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are 65.00wt%, 10.00wt% and 25.00wt% respectively), the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 75 ℃ for reaction for 6 hours, and then the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. The number average molecular weight of the obtained graft copolymer containing isocyanate groups is about 28410 and the weight average molecular weight is 72100 through GPC measurement; the resulting isocyanate group-containing graft copolymer had a viscous flow state temperature of about 170 ℃.
Example 3
Under the protection of nitrogen, 80g of ethyl methacrylate, 40g of butyl acrylate, 2g of mercaptoethanol serving as a chain transfer agent, 1.2g of azodiisoheptanonitrile serving as an initiator and 150g of ethyl acetate serving as a solvent are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 70 ℃, and after reaction for 5 hours, an ethyl acetate solution containing a polymer D is obtained; cooling the reaction system to room temperature, adding 0.01g of hydroquinone serving as a polymerization inhibitor, 0.02g of triethylamine serving as a catalyst and 5.0g of isocyanoethyl methacrylate (the molar ratio of the polymer D to the monomer E is 1: 1.25) serving as a monomer E containing carbon-carbon double bonds, stirring at room temperature for reaction for 10 hours, and then drying the product by rotary evaporation to obtain a high-molecular polymer C containing carbon-carbon double bonds; the number average molecular weight of the resulting high molecular polymer C was found to be about 11900 by GPC measurement.
Under the protection of nitrogen, 120g of methyl methacrylate, 15g of isocyanoethyl methacrylate, 15g of the prepared high molecular polymer C containing carbon-carbon double bonds, 1.2g of benzoyl peroxide and 150g of toluene are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are respectively 80.00wt%, 10.00wt% and 10.00 wt%), the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 80 ℃, the reaction is carried out for 8 hours, and the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. The resulting isocyanate group-containing graft copolymer had a number average molecular weight of about 58100 and a weight average molecular weight of 117200 as measured by GPC; the resulting isocyanate group-containing graft copolymer had a viscous state temperature of about 176 ℃.
Example 4
Under the protection of nitrogen, 60g of butyl methacrylate, 40g of methyl acrylate, 2g of a chain transfer agent, namely mercaptoacetic acid, 1.8g of an initiator, namely azobisisoheptonitrile, and 150g of a solvent, namely butyl acetate are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 70 ℃, and after reaction for 5 hours, a butyl acetate solution containing a polymer D is obtained; cooling to room temperature, adding 0.01g of hydroquinone serving as a polymerization inhibitor, 0.02g of triethylamine serving as a catalyst and 4.0g of glycidyl methacrylate monomer E containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 1.3), heating to 130 ℃, stirring for reaction for 12 hours, and then drying the product by rotary evaporation to obtain the high-molecular polymer C containing the carbon-carbon double bonds. The number average molecular weight of the resulting high molecular polymer C was about 9900 as determined by GPC measurement.
Under the protection of nitrogen, 10g of acrylonitrile, 30g of α -methyl styrene, 50g of methyl methacrylate, 5g of isocyanate ethyl acrylate, 5g of the prepared high molecular polymer C containing carbon-carbon double bonds, 2.1g of azobisisobutyronitrile and 100g of xylene are mixed and stirred uniformly (the using amounts of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are 90.00wt%, 5.00wt% and 5.00wt% respectively), the mixture is transferred into a four-neck flask provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 75 ℃, after reaction is carried out for 8 hours, the product is dried by rotary evaporation to obtain a graft copolymer containing isocyanate groups, and the number average molecular weight of the obtained graft copolymer containing the isocyanate groups is about 24800, the weight average molecular weight is 68600 and the viscous state temperature of the obtained graft copolymer containing the isocyanate groups is about 180 ℃.
Example 5
Under the protection of nitrogen, 70g of methyl methacrylate, 30g of ethyl acrylate, 2g of a chain transfer agent, namely mercaptoacetic acid, 2.1g of an initiator, namely azobisisoheptonitrile, and 120g of solvent, namely xylene are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 70 ℃, and after reaction for 5 hours, a xylene solution containing a polymer D is obtained; cooling to room temperature, adding 0.01g of hydroquinone serving as a polymerization inhibitor, 0.02g of triethylamine serving as a catalyst and 2.4g of glycidyl methacrylate monomer E containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 0.8), heating to 130 ℃, stirring for reaction for 12 hours, and then drying the product by rotary evaporation to obtain the high-molecular polymer C containing the carbon-carbon double bonds. The number average molecular weight of the resulting high molecular polymer C was found to be about 11300 by GPC measurement.
Under the protection of nitrogen, 70g of methyl methacrylate, 30g of butyl acrylate, 60g of isocyanoethyl methacrylate, 40g of the prepared high molecular polymer C containing carbon-carbon double bonds, 1.2g of benzoyl peroxide and 300g of toluene are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are respectively 50.00wt%, 30.00wt% and 20.00 wt%), the mixture is moved into a four-neck flask provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 85 ℃, the reaction is carried out for 8 hours, and the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. The number average molecular weight of the obtained graft copolymer containing isocyanate groups is about 39800 and the weight average molecular weight is 85600 through GPC test; the resulting isocyanate group-containing graft copolymer had a viscous state temperature of about 155 ℃.
Example 6
Under the protection of nitrogen, 115g of ethyl methacrylate, 5g of butyl acrylate, 4g of chain transfer agent thioglycolic acid, 2.4g of initiator dimethyl azodiisobutyrate and 120g of solvent butyl acetate are mixed and stirred uniformly, then the mixture is moved into a four-port bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 70 ℃, and after reaction for 5 hours, a butyl acetate solution containing a polymer D is obtained; heating to 130 ℃, adding 0.02g of hydroquinone serving as a polymerization inhibitor, 0.04g of tetramethylhexamethylenediamine serving as a catalyst and 4.8g of glycidyl methacrylate monomer E containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 0.8), stirring for reaction for 12 hours, and then evaporating and drying the product to obtain the high-molecular polymer C containing the carbon-carbon double bonds. The number average molecular weight of the resulting polymer C was about 10900 as determined by GPC measurement.
Under the protection of nitrogen, 130g of styrene, 45g of 3-isopropyl-dimethylbenzyl isocyanate, 25g of the prepared high molecular polymer C containing carbon-carbon double bonds, 1.8g of azobisisobutyronitrile and 200g of xylene are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are 65.00wt%, 22.50wt% and 12.50wt% respectively), the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 75 ℃, the reaction is carried out for 6 hours, and then the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. The number average molecular weight of the resulting isocyanate group-containing graft copolymer was about 34300 and the weight average molecular weight was 74100, as determined by GPC; the resulting isocyanate group-containing graft copolymer had a viscous flow state temperature of about 159 ℃.
Example 7
Under the protection of nitrogen, 80g of methyl methacrylate, 40g of isooctyl acrylate, 2.4g of mercaptododecanoic acid, 2.1g of azobisisobutyronitrile and 150g of butyl acetate are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 70 ℃, and after 5 hours of reaction, a butyl acetate solution containing polymer D is obtained; adding 0.02g of inhibitor hydroquinone and 1.6g of monomer E dimethylamino propyl methacrylamide containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 1), stirring for reacting for 8 hours, and then, drying the product by rotary evaporation to obtain the high molecular polymer C containing carbon-carbon double bonds. The number average molecular weight of the resulting polymer C was about 10900 as determined by GPC measurement.
Under the protection of nitrogen, 100g of methyl methacrylate, 50g of isooctyl acrylate, 30g of ethyl isocyanate acrylate, 20g of the prepared high molecular polymer C containing carbon-carbon double bonds, 1.2g of benzoyl peroxide and 150g of butyl acetate are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are 75.00wt%, 15.00wt% and 10.00wt% respectively), the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 85 ℃ for reaction for 10 hours, and then the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. The number average molecular weight of the resulting isocyanate group-containing graft copolymer was about 73100 and the weight average molecular weight was 143800 by GPC measurement; the resulting isocyanate group-containing graft copolymer had a viscous state temperature of about 115 ℃.
Example 8
Under the protection of nitrogen, 50g of methyl methacrylate, 50g of methyl acrylate, 2.4g of mercaptoethylamine, 4.4g of azobisisovaleronitrile and 280g of ethyl acetate are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 65 ℃, and after reaction for 7 hours, an ethyl acetate solution containing a polymer D is obtained; and cooling to room temperature, adding 0.02g of hydroquinone serving as a polymerization inhibitor and 4.8g of monomer E isocyanoethyl methacrylate containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 1), stirring at room temperature for reacting for 8 hours, and then drying the product by rotary evaporation to obtain the high-molecular polymer C containing the carbon-carbon double bonds. The number average molecular weight of the resulting high molecular polymer C was about 4300 as determined by GPC.
Under the protection of nitrogen, 80g of methyl methacrylate, 10g of isocyanoethyl methacrylate, 10g of the prepared high molecular polymer C containing carbon-carbon double bonds, 4.5g of azobisisobutyronitrile and 250g of toluene are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are respectively 80.00wt%, 10.00wt% and 10.00 wt%), the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 75 ℃, the reaction is carried out for 6 hours, and the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. The number average molecular weight of the obtained graft copolymer containing isocyanate groups is about 11300 and the weight average molecular weight is 36200 through GPC measurement; the resulting isocyanate group-containing graft copolymer had a viscous flow state temperature of about 167 ℃.
Example 9
Under the protection of nitrogen, 45g of methyl methacrylate, 55g of butyl acrylate, 1.2g of mercaptoethylamine, 1.8g of azobisisobutyronitrile and 150g of toluene are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 75 ℃, and after reaction for 6 hours, a toluene solution containing polymer D is obtained; adding 0.02g of hydroquinone serving as a polymerization inhibitor and 2.0g of glycidyl methacrylate monomer E containing carbon-carbon double bonds (the molar ratio of the polymer D to the monomer E is 1: 0.9), stirring for reacting for 6 hours, and then drying the product by rotary evaporation to obtain the high-molecular polymer C containing the carbon-carbon double bonds. The number average molecular weight of the resulting high molecular polymer C was about 8700 as determined by GPC measurement.
Under the protection of nitrogen, 65g of styrene, 20g of acrylonitrile, 25g of isocyanate ethyl acrylate, 10g of the prepared high molecular polymer C containing carbon-carbon double bonds, 1.2g of azobisisobutyronitrile and 80g of butyl acetate are mixed and stirred uniformly (the dosages of the monomer A, the monomer B and the high molecular polymer C containing carbon-carbon double bonds are 70.84wt%, 20.83wt% and 8.33wt% respectively), the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the mixture is heated to 75 ℃, the reaction is carried out for 6 hours, and the product is dried by rotary evaporation to obtain the graft copolymer containing isocyanate groups. The resulting isocyanate group-containing graft copolymer had a number average molecular weight of about 36700 and a weight average molecular weight of 88600 as determined by GPC; the resulting isocyanate group-containing graft copolymer had a viscous flow state temperature of about 184 ℃.
Comparative example 1
Under the protection of nitrogen, 100g of methyl methacrylate, 30g of butyl acrylate, 20g of isocyano ethyl methacrylate, 2.4g of initiator azobisisobutyronitrile and 250g of solvent toluene are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 75 ℃, the reaction is carried out for 6 hours, then the temperature is reduced to room temperature, and the product is subjected to rotary evaporation and drying to obtain the linear copolymer containing isocyanate groups. The resulting linear isocyanate group-containing copolymer had a number average molecular weight of about 14600 and a weight average molecular weight of 46100 as measured by GPC.
Comparative example 2
Under the protection of nitrogen, 100g of methyl methacrylate, 3.2g of chain transfer agent thioglycolic acid, 3g of initiator azobisisobutyronitrile and 200g of solvent toluene are mixed and stirred uniformly, then the mixture is moved to a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, heated to 65 ℃, reacted for 6 hours, cooled to room temperature, added with 0.01g of hydroquinone serving as a polymerization inhibitor, 0.04g of triethylamine serving as a catalyst and 5g of glycidyl methacrylate, stirred at 100 ℃ for 10 hours, and then the product is dried by rotary evaporation to obtain a high molecular polymer C containing carbon-carbon double bonds, wherein the number average molecular weight of the obtained high molecular polymer C is about 4100 according to GPC test.
Under the protection of nitrogen, 120g of methyl methacrylate, 20g of isocyano ethyl methacrylate, 10g of the prepared high molecular polymer C containing carbon-carbon double bonds, 2.4g of azobisisobutyronitrile and 250g of toluene are mixed and stirred uniformly, then the mixture is moved into a four-mouth bottle provided with a stirring paddle, a condenser and a thermometer, the temperature is heated to 75 ℃, after 6 hours of reaction, the product is dried by rotary evaporation, and then the comb-type graft copolymer containing isocyanate groups is obtained. The number average molecular weight of the resulting comb-graft copolymer containing isocyanate groups was approximately 14380 and the weight average molecular weight was 47460, as determined by GPC.
Performance testing
The isocyanate group-containing graft copolymers obtained in comparative example 1, comparative example 2 and examples 1 to 9 were applied as a compatibilizer for preparing ABS and polybutylene terephthalate (PBT) alloys, and compared with a commercially available compatibilizer. Wherein the ABS/PBT alloy formula comprises 63 parts of ABS, 35 parts of PBT and 2 parts of compatibilizer; the blank sample comprises 65 parts of ABS and 35 parts of PBT.
ABS and PBT are dried in an oven at 80 ℃ and 120 ℃ for 4 hours respectively for standby. Uniformly mixing all the materials, adding the materials into a feeding port of a double-screw extruder for extrusion granulation, sending extruded strips into a granulator for granulation after water cooling and blow drying through a water tank to obtain ABS/PBT alloy, drying the obtained alloy plastic particles for 4 hours at 80 ℃, adding the alloy plastic particles into a hopper of an injection molding machine, setting a corresponding injection molding process, and performing injection molding and film pressing molding to obtain a standard sample strip for testing. The test results are shown in table 1.
TABLE 1 ABS/PBT alloy Properties
Figure DEST_PATH_IMAGE004
As can be seen from Table 1, the ABS/PBT alloy material without the addition of the compatibilizer has poor compatibility and low notch impact strength, and the alloy product with the addition of the compatibilizer has improved compatibility and increased notch impact strength. It can be seen that the compatibilization effect of the isocyanate graft copolymer prepared by the invention is superior to that of the common compatibilizer on the market at present; compared with the comparative examples 1 and 2, the isocyanate group-containing graft copolymer compatibilizer prepared by the invention has better compatibilization effect than linear and comb structure compatibilizers obtained by the prior art under the conditions of similar molecular weight and isocyanate group content.
In addition, the melt index of the ABS/PBT alloy added with the isocyanate group-containing graft copolymer prepared by the invention is greatly reduced, the isocyanate group-containing graft copolymer reacts with hydroxyl in PBT for crosslinking, the molecular weight of the PBT is improved, and the isocyanate group-containing graft copolymer prepared by the invention also has the function of a chain extender.

Claims (14)

1. A graft copolymer containing isocyanate groups, which is a polymer containing isocyanate groups and high-molecular copolymer side chains and is prepared by the reaction of:
40 to 90 weight percent of monomer A containing carbon-carbon double bonds;
5 to 30 weight percent of unsaturated monomer B containing isocyanate group;
5wt% -30 wt% of high molecular polymer C containing carbon-carbon double bond;
the number average molecular weight of the graft copolymer containing isocyanate groups is 11000-73000, and the weight average molecular weight is 36000-144000;
the high molecular polymer C containing carbon-carbon double bonds is obtained by reacting a polymer D with a monomer E containing carbon-carbon double bonds, wherein the chemical general formula of the polymer D is as follows:
Figure FDA0002180786530000011
wherein R is1Is methyl, ethyl or butyl, R2Is a hydrogen atom or a methyl group, R3Is methyl, ethyl, propyl, butyl, tert-butyl or octyl when R is2When it is methyl, R1、R3Different; m is an integer of 20-100, k is an integer of 1-99, n is an integer of 1-100, and q is an integer of 2-12; s is sulfur atom, G is a group which reacts with the monomer E containing carbon-carbon double bond, and is one of carboxyl, amino or hydroxyl.
2. The isocyanate group-containing graft copolymer according to claim 1, which is obtained by reacting:
60-85 wt% of monomer A containing carbon-carbon double bond;
5 to 20 weight percent of unsaturated monomer B containing isocyanate group;
10 to 20 weight percent of high molecular polymer C containing carbon-carbon double bonds.
3. The graft copolymer containing isocyanate groups according to claim 1, wherein the number average molecular weight of the high molecular polymer C containing carbon-carbon double bonds is 4000 to 12000.
4. The graft copolymer containing isocyanate groups according to claim 1, wherein the monomer E containing a carbon-carbon double bond has an epoxy group, an amino group, an isocyanate group or an acid chloride group.
5. The isocyanate group-containing graft copolymer according to claim 4, wherein the carbon-carbon double bond-containing monomer E is one of acrylamide or methacrylamide, glycidyl methacrylate or allyl glycidyl ether, acryloyl chloride or methacryloyl chloride, methacryloyloxyethyl isocyanate, and derivatives thereof.
6. The graft copolymer containing isocyanate groups according to claim 1, wherein the molar ratio of the polymer D to the monomer E containing a carbon-carbon double bond is 1:0.8 to 1.3.
7. The isocyanate group-containing graft copolymer according to claim 1, wherein the monomer A having a carbon-carbon double bond is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, styrene, α -methylstyrene, α -ethylstyrene, acrylonitrile, methacrylonitrile, and derivatives thereof.
8. The isocyanate group-containing graft copolymer according to claim 1, wherein the isocyanate group-containing unsaturated monomer B is one or more of isocyanoethyl methacrylate, 3-isopropyl-dimethylbenzyl isocyanate, ethyl isocyanate acrylate, and derivatives thereof.
9. The graft copolymer containing isocyanate groups according to claim 1, wherein the polymer D is prepared by radical polymerization of a plurality of acrylate or methacrylate monomers with a chain transfer agent initiated by an initiator; the chain transfer agent is one of aliphatic mercaptan containing carboxyl, hydroxyl or amino; the initiator is one of azo initiator, peroxide initiator or redox initiator.
10. The graft copolymer containing isocyanate groups according to claim 1, wherein the graft copolymer containing isocyanate groups is prepared by copolymerizing a monomer A containing a carbon-carbon double bond, an unsaturated monomer B containing isocyanate groups and a high molecular polymer C containing a carbon-carbon double bond by a radical polymerization method.
11. The isocyanate group-containing graft copolymer according to claim 10, wherein the radical polymerization method is solution polymerization.
12. The isocyanate group-containing graft copolymer according to claim 1, wherein the isocyanate group-containing graft copolymer has a viscous state temperature of 110 to 200 ℃.
13. The isocyanate group-containing graft copolymer according to claim 1, wherein the isocyanate group-containing graft copolymer has a viscous state temperature of 140 to 180 ℃.
14. Use of the isocyanate group-containing graft copolymer according to any one of claims 1 to 13 as a compatibilizer for polymer blends and as a chain extender for polymers.
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