CN108239234A - A kind of graft copolymer and its application containing epoxy group - Google Patents
A kind of graft copolymer and its application containing epoxy group Download PDFInfo
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- CN108239234A CN108239234A CN201611226765.2A CN201611226765A CN108239234A CN 108239234 A CN108239234 A CN 108239234A CN 201611226765 A CN201611226765 A CN 201611226765A CN 108239234 A CN108239234 A CN 108239234A
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- 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
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- 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
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- C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
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- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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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- C08F8/00—Chemical modification by after-treatment
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- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention discloses a kind of graft copolymer containing epoxy group and its application.The graft copolymer is a kind of polymer containing epoxy group and high-molecular copolymer side chain, is mainly copolymerized by the high molecular polymer C of monomer A, 5wt% ~ 30wt% of 40wt% ~ 90wt% carbon-carbon double bonds unsaturated monomer B, 5wt% containing epoxy group ~ 30wt% carbon-carbon double bonds by free radical polymerization.Preparation process is：High molecular polymer D is obtained first with free-radical polymerized, the high molecular polymer C of carbon-carbon double bonds is then prepared using the reaction between group；The high molecular polymer C of acquisition and monomer A, monomer B are finally carried out to free-radical polymerized, graft copolymer of the acquisition containing epoxy group after dry devolatilization.Graft copolymer of the present invention containing epoxy group can be as the bulking agent of polymer blend and the chain extender of polymer.
Description
Technical field
Synthesis and application field the present invention relates to graft copolymer, and in particular to a kind of acrylate containing epoxy group
Graft copolymer and its application.
Background technology
Bulking agent refers to using means physically or chemically, incompatible co-mixing system be promoted to be combined together, and then obtain
To the auxiliary agent for stablizing co-mixing system.For polymer blend, due between each component in chemical constitution, polarity, molecular weight
（Viscosity）It causes to be separated with the difference in crystallinity, leads to the poor performance of polymer blend.Therefore, bulking agent is high level
The foundation stone of blending and modifying product.Particularly in current raw material and modified materials market, the factory formula of enterprise and technological process
Come into the open mostly, transparence, the addition of bulking agent then becomes the key point of material modification manufacturer and rival's differentiation.
For the polymer blend containing reactive group in system, usually using reactive compatibilizer.Common reaction
Type bulking agent is mostly Graft copolymer, such as PP grafted maleic anhydrides（102924661 B, CN 101519477 of Chinese patent CN
B）, styrene-grafted maleic anhydride（102993350 B of Chinese patent CN）, ABS grafted maleic anhydrides etc..This kind of bulking agent is more
The method squeezed out using frit reaction, the grafting functional group on polymer molecular chain obtain graft reaction type bulking agent, raw
Production. art is simpler.Although this kind of bulking agent can solve the problems, such as polymer blend compatibility to a certain extent, due to work
Skill limits, and single varieties, grafting rate is low, mostly acid anhydrides type bulking agent.Compared with anhydride bulking agent, epoxies bulking agent and carboxylic
Base and hydroxyl have higher reactivity, have better compatibilization effect in polyester alloy.It is connect to obtain epoxy group
The bulking agent of branch, 102492101 A of Chinese patent CN disclose a kind of by glycidyl methacrylate（GMA）It is grafted to
Method on ABS resin using the technique of fusion-grafting, can obtain the graft with epoxy group, although method is simple,
Side reaction is more, and reaction is difficult to control, and epoxy grafting rate highest only has 0.67%.Additive amount is larger in actual use, increase-volume efficiency
Low, therefore, the bulking agent that fusion-grafting method obtains tends not to meet actual demand.
In order to realize effective control to bulking agent structure and grafting rate, patent of invention of the E.I.Du Pont Company early in 1973
Ethylene-butyl acrylate-glycidyl methacrylate is just prepared using the method for copolymerization in US3723570（PTW）Ternary
Copolymer compatibilizing agent.On this basis, 101851321 B of Chinese patent CN use the technique of suspension polymerisation, are prepared for ternary and are total to
Polymers bulking agent styrene-acrylonitrile-glycidyl methacrylate（SAG）Bulking agent, can be with control ring by this method
The content of oxygen groups, obtains the bulking agent product of high grafting rate, and the grafting rate of epoxy group can be up to 10%.Due in system
Containing styrene and acrylonitrile unit, therefore the bulking agent is especially suitable for ABS class alloy systems.Compared with other bulking agents,
The bulking agent can effectively improve ABS and polyethylene terephthalate（PET）The compatibility of alloy（CN 102181122 A）
With makrolon and the thermal stability of ABS alloy（CN 104877326 A）.
The structure of more than bulking agent is mostly line style bulking agent, in practical applications, the reactive group content of high grafting rate
Can improve the compatibility with a wherein phase, but the winding of molecule interchain can only be often relied on another phase, active force compared with
It is weak.And by adjusting bulking agent structure, while reactive group grafting rate is ensured, introduced and another phase on its main chain
The polymer segment of thermodynamic compatibility can effectively improve winding and the two alternate compatibilities of molecule interchain.Chinese patent
103421154 A of CN disclose a kind of comb-grafted copolymer containing reactive group and its preparation method and application.The patent
By introducing polyacrylate homopolymers segment on polymer lateral chain, using free-radical polymerized method, high grafting is obtained
The comb-shaped polymer of rate.Compared with the bulking agent of commercialization, which can effectively improve the modulus of PET/ABS alloys, fracture
Elongation, yield strength and tensile strength etc. have the better increase-volume efficiency of higher than the line style bulking agent of identical grafting rate（WY
Dong, HT Wang, MF He, et al. Synthesis of Reactive Comb Polymers and Their
Applications as a Highly Efficient Compatibilizer in Immiscible Polymer
Blends [J]. Industrial & Engineering Chemistry Research, 2015, 54: 2081-
2089）.The comb-grafted copolymer that the patent of invention obtains also has chain extension effect.Nevertheless, bulking agent side in the patent
The polymer segment of chain is mainly the homopolymer of methyl acrylic ester or acrylic ester monomer, in practical applications side chain with
Another phase tends not to compatible well.Homopolymer single on bulking agent side chain has specific polarity and solubility simultaneously
Parameter also limits its application to a certain extent.
Invention content
It is an object of the invention to be directed to the deficiency of existing polymer blend capacity increasing technique, a kind of new and effective contain is provided
The graft copolymer of epoxy group.
The present invention also aims to provide the graft copolymer containing epoxy group as polymer blend bulking agent
And the application of polymer chain extender.
The object of the invention is achieved through the following technical solutions：
A kind of graft copolymer containing epoxy group, the graft copolymer are containing epoxy group and high-molecular copolymer side chain
A kind of polymer is made by following substance reaction：
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 30wt% containing epoxy group；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing epoxy group is 10000 ~ 100000, weight average molecular weight for 34000 ~
200000。
The present invention using carbon-carbon double bonds high molecular polymer C and carbon-carbon double bonds monomer A, containing epoxy group not
The graft copolymer containing epoxy group is obtained by the reaction in saturation monomer B.As bulking agent in use, the epoxy group of high grafting rate contains
Amount can improve the compatibility with a wherein phase, and the high molecular polymer C of carbon-carbon double bonds is as graft copolymerization in the present invention
The side chain of object, introduces copolymer, by adjust different monomers selection and proportioning, it can be achieved that side chain strand compliance
Control, but also the solubility parameter of side chain polymer segment can be adjusted, preferably improve bulking agent and the phase of another phase
Capacitive enhances two alternate binding forces.The height that graft copolymer containing epoxy group prepared by the present invention is obtained with the prior art connects
Branch rate line style is compared with the bulking agent of comb-type structure, has better increase-volume effect in the case of close molecular weight and grafting rate
Fruit can be used as bulking agent and polymer chain extender to use.
The graft copolymer containing epoxy group, is made by following substance reaction：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing epoxy group；
The high molecular polymer C of 10wt% ~ 20wt% carbon-carbon double bonds.
The high molecular polymer C of the carbon-carbon double bonds is obtained by the reaction by the monomer E of polymer D and carbon-carbon double bonds, institute
Stating polymer D chemical general formulas is：
Wherein R1For methyl, ethyl or butyl, R2For hydrogen atom or methyl, R3For methyl, ethyl, propyl, butyl, tertiary butyl or
Octyl group works as R2During for methyl, R1、R3It is different；M is 20 ~ 100 integer, and k is 1 ~ 99 integer, and n is 1 ~ 100 integer, q for 2 ~
12 integer；S is sulphur atom, and G is the group reacted with the monomer E of carbon-carbon double bonds, is in carboxyl, amino or hydroxyl
It is a kind of.
Preferably, the high molecular polymer C number-average molecular weights of the carbon-carbon double bonds are 4000 ~ 12000.
The high molecular polymer C glass transition temperatures of the carbon-carbon double bonds are 10 DEG C ~ 100 DEG C.
The monomer E of the carbon-carbon double bonds carries epoxy group, amino, isocyanate group or acid chloride group.
Preferably, the monomer E of the carbon-carbon double bonds is sweet for acrylamide or Methacrylamide, Glycidyl methacrylate
Grease or allyl glycidyl ether, acryloyl chloride or methacrylic chloride, methylacryoyloxyethyl isocyanates and its spread out
One kind in biology.
The molar ratio of the polymer D and the monomer E of carbon-carbon double bonds are 1:0.8~1.3.
The monomer A of the carbon-carbon double bonds for methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Isooctyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, styrene, Alpha-Methyl
It is one or more in styrene, α-ethyl styrene, acrylonitrile, methacrylonitrile and its derivative.
The unsaturated monomer B containing epoxy group for glycidyl methacrylate, allyl glycidyl ether and
It is one or more in its derivative.
The polymer D is led to by the one or more and chain-transferring agent in esters of acrylic acid or methacrylate-based monomer
Initiator initiation free radical polymerization is crossed to be made；The chain-transferring agent is in the aliphatic mercaptan containing carboxyl, hydroxyl or amino
It is a kind of；The initiator is one kind in azo-initiator, peroxide initiator or redox initiator.
The graft copolymer containing epoxy group is by the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing epoxy group
It is copolymerized with the high molecular polymer C of carbon-carbon double bonds by free radical polymerisation process.
The free radical polymerisation process is one kind in bulk polymerization, polymerisation in solution, suspension polymerisation or emulsion polymerization.
The graft copolymer viscous state temperature containing epoxy group is 110 DEG C ~ 200 DEG C.
Preferably, the graft copolymer viscous state temperature containing epoxy group is 140 DEG C ~ 180 DEG C.
The graft copolymer containing epoxy group can be by the particle of pelleter, comminutor making；It can also be powder
The powder that broken mechanism is made.
The graft copolymer containing epoxy group can be as the bulking agent of polymer blend and the chain extender of polymer.
Compared with prior art, the present invention has the advantages that：
Graft copolymer containing epoxy group prepared by the present invention is used as bulking agent, and the epoxy group content of high grafting rate can
To improve the compatibility with a wherein phase, the copolymer for the polyacrylate that side chain introduces passes through different acrylate monomer
The control to side chain strand compliance can be achieved in selection and proportioning, moreover it is possible to the solubility parameter of side chain polymer segment is adjusted,
Graft copolymer and the compatibility of another phase are preferably improved, enhances two alternate binding forces.The height obtained with the prior art connects
Branch rate line style is compared with the bulking agent of comb-type structure, is had in the case of similar molecular weight and epoxy group content better
Compatibilization effect.Graft copolymer containing epoxy group prepared by the present invention can also be crosslinked with polymer to react, and improves poly-
Adduct molecule amount, plays chain extender；Compared with common linear polymer chain extender, what the present invention obtained connects containing epoxy group
Graft copolymer has higher molecular weight, and chain extension effect becomes apparent.
Description of the drawings
Fig. 1 is the infrared spectrum of the graft copolymer containing epoxy group prepared in embodiment 1.
Fig. 2 is the GPC spectrograms of the graft copolymer containing epoxy group prepared in embodiment 1.
Specific embodiment
The present invention being further expalined explanation with reference to specific embodiment, description is more specific and detailed, but
Can not the limitation to the scope of the claims of the present invention therefore be interpreted as, as long as the form using equivalent substitution or equivalent transformation is obtained
The technical solution obtained, should all be included within the protection domain of the claims in the present invention.
In following embodiment, raw material used is commercial goods.
Test and characterizing method
（One）Examination of infrared spectrum
Tabletting after the graft copolymer containing epoxy group of acquisition is milled with dried potassium bromide, is placed on Fourier transform
Infrared spectrometer is tested.4000 ~ 400cm of scanning range-1, resolution ratio 4cm-1, scanning times 16 times.
（Two）Gel permeation chromatography（GPC）Test
After the graft copolymer containing epoxy group of acquisition is dissolved with tetrahydrofuran, measured and polymerize using gel permeation chromatograph
The retention time of object, detecting instrument are refraction index analyzer, and mobile phase is tetrahydrofuran, using monodisperse polystyrene conduct
Standard specimen calculates the relative molecular weight of polymer and its distribution.
（Three）Viscous state temperature test
By the graft copolymer containing epoxy group of acquisition after heating melts, the thin slice that thickness is about 2mm is made, and use
Thermomechanical analyzer（TMA）The temperature strain curve of copolymer is tested, the viscosity flow of copolymer is obtained according to temperature strain curve
State temperature.
Embodiment 1
Under nitrogen protection, 80g methyl methacrylates, 20g ethyl acrylates, 1.5g chain-transferring agents mercaprol, 4.5g are drawn
After hair agent azodiisobutyronitrile and 200g solvent toluenes are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
In four-hole bottle, 65 DEG C are heated to, after reacting 6h, obtains the toluene solution of the D containing polymer；Reaction system is down to room temperature, is added in
The monomer E metering systems of 0.01g hydroquinone of polymerization retarder, 0.04g catalyst ns, N- dimethyl benzylamines and 2.1g carbon-carbon double bonds
Acyl chlorides（Polymer D is 1 with monomer E molar ratios:1.2）, after reaction 8h is stirred at room temperature, after product revolving drying, obtain carbon containing
The high molecular polymer C of carbon double bond, the number-average molecular weight of high molecular polymer C for understanding to obtain by GPC tests is about 4200.
Nitrogen protection under, by 80g methyl methacrylates, 40g butyl acrylates, 20g glycidyl methacrylate,
High molecular polymer C, 4.5g azodiisobutyronitrile and 150g toluene of the carbon-carbon double bonds of the above-mentioned preparations of 10g are mixed evenly
Afterwards（The high molecular polymer C dosages of monomer A, monomer B and carbon-carbon double bonds be respectively 80.00wt%, 13.33wt% and
6.67wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 75 DEG C, after reacting 6h, product is revolved
Be evaporated it is dry after, obtain graft copolymer.By infrared spectrum it is found that as shown in Figure 1, obtained graft copolymer contains epoxy group
Group；It is tested by GPC, as can be seen from Figure 2, graft copolymer number-average molecular weight of the gained containing epoxy group is about 18132, is divided equally again
Son amount is 50710；Graft copolymer viscous state temperature of the gained containing epoxy group is about 158 DEG C.
Embodiment 2
Under nitrogen protection, 60g methyl methacrylates, 50g butyl acrylates, 1.5g chain-transferring agents mercaprol, 3.5g are drawn
After hair agent azodiisobutyronitrile and 250g solvent xylenes are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in, be heated to 65 DEG C, after reacting 6h, obtain the xylene solution of the D containing polymer；Reaction system is down to room temperature,
Add in the monomer E methacrylic chlorides of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 2.1g carbon-carbon double bonds
（Polymer D is 1 with monomer E molar ratios:1.2）, after reaction 5h is stirred at room temperature, after product revolving drying, obtain carbon-carbon double
The high molecular polymer C of key.The number-average molecular weight of high molecular polymer C for understanding to obtain by GPC tests is about 5100.
It is under nitrogen protection, 110g styrene, 20g ethyl acrylates, 16g glycidyl methacrylate, 54g is above-mentioned
After high molecular polymer C, 2.1g azodiisobutyronitrile and 300g butyl acetates of the carbon-carbon double bonds of preparation are mixed evenly
（The high molecular polymer C dosages of monomer A, monomer B and carbon-carbon double bonds are respectively 65.00wt%, 8.00wt% and 27.00wt%）,
It moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, is heated to 75 DEG C, after reacting 6h, after product revolving drying,
Obtain graft copolymer.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, gained contains
The graft copolymer number-average molecular weight of epoxy group is about 26410, weight average molecular weight 77800；Gained connecing containing epoxy group
Graft copolymer viscous state temperature is about 169 DEG C.
Embodiment 3
Under nitrogen protection, 80g ethyl methacrylate, 40g butyl acrylates, 2g chain-transferring agents mercaptoethanol, 1.2g are caused
After agent azobisisoheptonitrile and 150g solvent ethyl acetates are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in, be heated to 70 DEG C, after reacting 5h, obtain the ethyl acetate solution of the D containing polymer；Reaction system is down to room
Temperature adds in the monomer E methacrylic acids of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 5.0g carbon-carbon double bonds
Isocyano group ethyl ester（Polymer D is 1 with monomer E molar ratios:1.25）, after reaction 10h is stirred at room temperature, after product revolving drying,
Obtain the high molecular polymer C of carbon-carbon double bonds.The obtained number-average molecular weight of high molecular polymer C is understood by GPC tests
About 11900.
Under nitrogen protection, by 120g methyl methacrylates, 15g glycidyl methacrylate, 15g above-mentioned preparations
After high molecular polymer C, 1.6g benzoyl peroxide and 150g butanone of carbon-carbon double bonds are mixed evenly（Monomer A, monomer
The high molecular polymer C dosages of B and carbon-carbon double bonds are respectively 80.00wt%, 10.00wt% and 10.00wt%）, move to be equipped with and stir
In the four-hole bottle for mixing paddle, condenser and thermometer, 80 DEG C are heated to, after reacting 8h, after product revolving drying, obtains grafting altogether
Polymers.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, gained is containing epoxy group
Graft copolymer number-average molecular weight is about 52900, weight average molecular weight 121100；Graft copolymer of the gained containing epoxy group glues
Fluidised form temperature is about 175 DEG C.
Embodiment 4
Under nitrogen protection, 50g butyl methacrylates, 50g methyl acrylates, 2g chain-transferring agents thioacetic acid, 1.6g are caused
After agent azobisisoheptonitrile and 150g solvent acetic acid butyl esters are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in, be heated to 70 DEG C, after reacting 5h, obtain the butyl acetate solution of the D containing polymer；Room temperature is down to, adds in 0.01g
The monomer E glycidyl methacrylate of hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 4.0g carbon-carbon double bonds
（Polymer D is 1 with monomer E molar ratios:1.3）, be warming up to 130 DEG C be stirred to react 12h after, by product revolving it is dry after, obtain
The high molecular polymer C of carbon-carbon double bonds.It is about by the number-average molecular weight of high molecular polymer C obtained knowable to GPC tests
10700。
Under nitrogen protection, 10g acrylonitrile, 30g α-methylstyrenes, 50g methyl methacrylates, 5g pi-allyls are contracted
High molecular polymer C, 1.6g azodiisobutyronitrile and 100g the toluene mixing of the carbon-carbon double bonds of the above-mentioned preparation of water glycerin ether, 5g
After stirring evenly（The high molecular polymer C dosages of monomer A, monomer B and carbon-carbon double bonds be respectively 90.00wt%, 5.00wt% and
5.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 75 DEG C, after reacting 8h, product is revolved
Be evaporated it is dry after, obtain graft copolymer.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；It is surveyed by GPC
Examination, graft copolymer number-average molecular weight of the gained containing epoxy group is about 29700, weight average molecular weight 76600；Gained contains epoxy
The graft copolymer viscous state temperature of group is about 178 DEG C.
Embodiment 5
Under nitrogen protection, 60g methyl methacrylates, 40g methyl acrylates, 2g chain-transferring agents thioacetic acid, 1.8g are caused
After agent azobisisoheptonitrile and 120g solvent xylenes are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
In four-hole bottle, 70 DEG C are heated to, after reacting 5h, obtains the xylene solution of the D containing polymer；Room temperature is down to, adds in 0.01g inhibitions
The monomer E glycidyl methacrylate of agent hydroquinone, 0.02g catalyst of triethylamine and 2.4g carbon-carbon double bonds（Polymerization
Object D is 1 with monomer E molar ratios:0.8）, be warming up to 130 DEG C be stirred to react 12h after, by product revolving it is dry after, obtain carbon containing carbon
The high molecular polymer C of double bond.The number-average molecular weight of high molecular polymer C for understanding to obtain by GPC tests is about 11800.
Nitrogen protection under, by 70g methyl methacrylates, 30g butyl acrylates, 60g glycidyl methacrylate,
High molecular polymer C, 1.5g benzoyl peroxide and 300g toluene of the carbon-carbon double bonds of the above-mentioned preparations of 40g are mixed evenly
Afterwards（The high molecular polymer C dosages of monomer A, monomer B and carbon-carbon double bonds be respectively 50.00wt%, 30.00wt% and
20.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 85 DEG C, after reacting 8h, by product
After revolving is dry, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；By GPC
Test, graft copolymer number-average molecular weight of the gained containing epoxy group is about 42100, weight average molecular weight 97500；Gained contains ring
The graft copolymer viscous state temperature of oxygen groups is about 147 DEG C.
Embodiment 6
Under nitrogen protection, 115g ethyl methacrylate, 5g butyl acrylates, 4 g chain-transferring agents thioacetic acid, 2.8g are caused
After agent azo-bis-iso-dimethyl and 120g solvent acetic acid butyl esters are mixed evenly, move to equipped with agitating paddle, condenser and
In the four-hole bottle of thermometer, 70 DEG C are heated to, after reacting 5h, obtains the butyl acetate solution of the D containing polymer；130 DEG C are warming up to,
Add in the monomer E methyl-props of 0.02g hydroquinone of polymerization retarder, 0.04g catalyst 4-methyl hexamethylene diamine and 4.8 g carbon-carbon double bonds
Olefin(e) acid ethylene oxidic ester（Polymer D is 1 with monomer E molar ratios:0.8）, after being stirred to react 12h, after product revolving drying, obtain
To the high molecular polymer C of carbon-carbon double bonds.The obtained number-average molecular weight of high molecular polymer C is understood about by GPC tests
It is 9300.
Under nitrogen protection, by 130g styrene, 45g allyl glycidyl ethers, 25g above-mentioned preparations carbon-carbon double bonds
After high molecular polymer C, 1.8g azodiisobutyronitrile and 200g dimethylbenzene are mixed evenly（Monomer A, monomer B and carbon containing carbon
The high molecular polymer C dosages of double bond are respectively 65.00wt%, 22.50wt% and 12.50wt%）, move to equipped with agitating paddle, condensation
In the four-hole bottle of device and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, obtains graft copolymer.By red
External spectrum is it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, graft copolymerization of the gained containing epoxy group
Object number-average molecular weight is about 31520, weight average molecular weight 76800；Graft copolymer viscous state temperature of the gained containing epoxy group
About 156 DEG C.
Embodiment 7
Under nitrogen protection, by 80g methyl methacrylates, 30g Isooctyl acrylate monomers, 2.4g sulfydryls lauric acid/dodecanoic acid, 1.8g azos two
After isobutyronitrile and 150g butyl acetates are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, add
Heat after reacting 5h, obtains the butyl acetate solution of the D containing polymer to 70 DEG C；It adds in 0.02g hydroquinone of polymerization retarder and 1.6g contains
The monomer E dimethylamino-propyl Methacrylamides of carbon-carbon double bond（Polymer D is 1 with monomer E molar ratios:1）, it is stirred to react 8h
Afterwards, by after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Obtained macromolecule is understood by GPC tests
The number-average molecular weight of polymer C is about 10500.
Under nitrogen protection, by 100g methyl methacrylates, 50 Isooctyl acrylate monomers, 30g methyl propenoic acid glycidyls
High molecular polymer C, 1.5g benzoyl peroxide and 150g the butyl acetates mixing of the carbon-carbon double bonds of the above-mentioned preparation of ester, 20g
After stirring evenly（The high molecular polymer C dosages of monomer A, monomer B and carbon-carbon double bonds are respectively 75.00wt%, 15.00wt%
And 10.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 85 DEG C, after reacting 10h, will produce
After object revolving is dry, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；By
GPC is tested, and graft copolymer number-average molecular weight of the gained containing epoxy group is about 69100, weight average molecular weight 141100；Gained
Graft copolymer viscous state temperature containing epoxy group is about 118 DEG C.
Embodiment 8
Under nitrogen protection, by 40g methyl methacrylates, 60g methyl acrylates, 2.4g mercaptoethylmaines, 4.2g azo diisoamyls
After nitrile and 250g ethyl acetate are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to
65 DEG C, after reacting 7h, obtain the ethyl acetate solution of the D containing polymer；Be down to room temperature, add in 0.02g hydroquinone of polymerization retarder and
The monomer E isocyanatoethyls of 4.8g carbon-carbon double bonds（Polymer D is 1 with monomer E molar ratios:1）, it is stirred at room temperature
After reacting 8h, after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Understand what is obtained by GPC tests
The number-average molecular weight of high molecular polymer C is about 4500.
Under nitrogen protection, by 80g methyl methacrylates, 10g glycidyl methacrylate, 10g above-mentioned preparations
After high molecular polymer C, 4.5g azodiisobutyronitrile and 200g toluene of carbon-carbon double bonds are mixed evenly（Monomer A, monomer
The high molecular polymer C dosages of B and carbon-carbon double bonds are respectively 80.00wt%, 10.00wt% and 10.00wt%）, move to be equipped with and stir
In the four-hole bottle for mixing paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, obtains grafting altogether
Polymers.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, gained is containing epoxy group
Graft copolymer number-average molecular weight is about 10200, weight average molecular weight 34400；Graft copolymer of the gained containing epoxy group glues
Fluidised form temperature is about 170 DEG C.
Embodiment 9
Under nitrogen protection, by 40g methyl methacrylates, 60g butyl acrylates, 1.2g mercaptoethylmaines, two isobutyl of 2.1g azos
After nitrile and 150g toluene are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 75
DEG C, after reacting 6h, obtain the toluene solution of the D containing polymer；Add in 0.02g hydroquinone of polymerization retarder and 2.0g carbon-carbon double bonds
Monomer E glycidyl methacrylate（Polymer D is 1 with monomer E molar ratios:0.9）, after being stirred to react 6h, product is revolved
Be evaporated it is dry after, obtain the high molecular polymer C of carbon-carbon double bonds.The obtained number of high molecular polymer C is understood by GPC tests
Average molecular weight is about 7400.
Nitrogen protection under, by 65g styrene, 25g acrylonitrile, 5g allyl glycidyl ethers, the above-mentioned preparations of 5g it is carbon containing
After high molecular polymer C, 1.5g azodiisobutyronitrile and 80g butyl acetates of carbon double bond are mixed evenly（Monomer A, monomer B
High molecular polymer C dosages with carbon-carbon double bonds are respectively 90.00wt%, 5.00wt% and 5.00wt%）, move to equipped with stirring
In the four-hole bottle of paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, obtains graft copolymerization
Object.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, gained connecing containing epoxy group
Graft copolymer number-average molecular weight is about 33400, weight average molecular weight 86500；Graft copolymer viscosity flow of the gained containing epoxy group
State temperature is about 178 DEG C.
Embodiment 10
Under nitrogen protection, 60g methyl methacrylates, 50g ethyl acrylates, 1.5g chain-transferring agents mercaprol, 3.5g are drawn
After hair agent azodiisobutyronitrile and 250g solvent toluenes are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
In four-hole bottle, 65 DEG C are heated to, after reacting 6h, obtains the toluene solution of the D containing polymer；Reaction system is down to room temperature, is added in
The monomer E metering systems of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst ns, N- dimethyl benzylamines and 2.1g carbon-carbon double bonds
Acyl chlorides（Polymer D is 1 with monomer E molar ratios:1.2）, after reaction 5h is stirred at room temperature, after product revolving drying, obtain carbon containing
The high molecular polymer C of carbon double bond, the number-average molecular weight of high molecular polymer C for understanding to obtain by GPC tests is about 5100.
By 80g styrene, 18g butyl acrylates, 10g glycidyl methacrylate, the above-mentioned preparations of 12g carbon containing carbon
The high molecular polymer C of double bond, 2.4 g anion emulsifiers lauryl sodium sulfate, 1.2g nonionic emulsifier polyoxyethylene
Homogenizer high-speed stirred 15min is used after octyl phenol ether, 0.75g initiator potassium persulfates and the mixing of 175g distilled water,
Obtain pre-emulsion（The high molecular polymer C dosages of monomer A, monomer B and carbon-carbon double bonds are respectively 81.67wt%, 8.33wt%
And 10.00wt%）；The pre-emulsion of acquisition is moved in the four-hole bottle equipped with agitating paddle, condenser and thermometer, nitrogen atmosphere
Protection is heated to 75 DEG C, after reacting 8h, is cooled to room temperature, and adds in the CaCl of 10 ml a concentration of 5%2Aqueous solution, after demulsification precipitates
Product is washed repeatedly with distilled water, is crushed after then drying, obtains graft copolymer.By infrared spectrum it is found that is obtained connects
Graft copolymer contains epoxy group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing epoxy group is about
89100, weight average molecular weight 197100；Graft copolymer viscous state temperature of the gained containing epoxy group is about 173 DEG C.
Embodiment 11
Under nitrogen protection, by 40g methyl methacrylates, 60g methyl acrylates, 2.4g mercaptoethylmaines, 4.2g azo diisoamyls
After nitrile and 250g ethyl acetate are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to
65 DEG C, after reacting 7h, room temperature is down to, obtains the ethyl acetate solution of the D containing polymer；Add in 0.02g hydroquinone of polymerization retarder and
The monomer E isocyanatoethyls of 4.8g carbon-carbon double bonds（Polymer D is 1 with monomer E molar ratios:1）, it is stirred at room temperature
After reacting 8h, after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Understand what is obtained by GPC tests
The number-average molecular weight of high molecular polymer C is about 4500.
2g calcium phosphate and 2g sodium sulphate are dissolved in 150g distilled water, moved to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in；By 80g methyl methacrylates, 10g allyl glycidyl ethers, 1.5g initiators (NH4)2S2O8-FeSO4、
The high molecular polymer C of the carbon-carbon double bonds of the above-mentioned preparations of 30g is after mixing（The height of monomer A, monomer B and carbon-carbon double bonds
Molecularly Imprinted Polymer C dosages are respectively 66.67wt%, 8.33wt% and 25.00wt%）, add in above-mentioned four-hole bottle, nitrogen atmosphere is protected
Shield is heated to 65 DEG C, after reacting 7h, product is washed and is filtered, graft copolymer is obtained after dry.By infrared spectrum it is found that obtaining
To graft copolymer contain epoxy group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing epoxy group is about
It is 92900, weight average molecular weight 174100；Graft copolymer viscous state temperature of the gained containing epoxy group is about 193 DEG C.
Comparative example 1
Nitrogen protection under, by 100g methyl methacrylates, 30g butyl acrylates, 20g glycidyl methacrylate,
After 2.1g initiator azodiisobutyronitriles and 200g solvent toluenes are mixed evenly, move to equipped with agitating paddle, condenser and temperature
It spends in the four-hole bottle of meter, is heated to 75 DEG C, after reacting 6h, be down to room temperature, after product revolving drying, obtain linear copolymers.
By infrared spectrum it is found that obtained linear copolymers contain epoxy group；It is tested by GPC, line style of the gained containing epoxy group
Copolymer number-average molecular weight is about 17920, weight average molecular weight 51800.
Comparative example 2
Under nitrogen protection, by 100g methyl methacrylates, 3.2g chain-transferring agents thioacetic acid, 3g initiator azodiisobutyronitriles
After being mixed evenly with 200g solvent toluenes, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 65
DEG C, after reacting 6h, room temperature is down to, adds in 0.01g hydroquinone of polymerization retarder, 0.04g catalyst of triethylamine and 5g methacrylic acids
Ethylene oxidic ester after 100 DEG C are stirred to react 10h, after product revolving drying, obtains the high molecular polymer C of carbon-carbon double bonds,
The number-average molecular weight of high molecular polymer C for understanding to obtain by GPC tests is about 4100.
Under nitrogen protection, by 120g methyl methacrylates, 20g glycidyl methacrylate, 10g above-mentioned preparations
After high molecular polymer C, 1.5g azodiisobutyronitrile and 250g toluene of carbon-carbon double bonds are mixed evenly, move to be equipped with and stir
In the four-hole bottle for mixing paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, combed is obtained and connects
Graft copolymer.By infrared spectrum it is found that obtained comb-grafted copolymer contains epoxy group；It is tested by GPC, gained contains ring
The comb-grafted copolymer number-average molecular weight of oxygen groups is about 18220, weight average molecular weight 50670.
Application performance test
Using the graft copolymer containing epoxy group obtained in comparative example 1, comparative example 2 and embodiment 1-11 as bulking agent application
In preparation ABS and polybutylene terephthalate (PBT)（PBT）Alloy, and compared with Commercial epoxy class bulking agent.Wherein ABS/PBT
63 parts of ABS in alloy formula, 35 parts of PBT, 2 parts of bulking agent；Blank sample is 65 parts of ABS, 35 parts of PBT.
Raw material A BS and PBT dry 4h in 80 DEG C and 120 DEG C of baking ovens respectively, spare.It is double that each material is uniformly mixed addition
Screw extruder spout extruding pelletization, squeeze out material strip by sink it is water cooled, drying after be sent into pelleter pelletizing obtain ABS/
PBT alloy by 80 DEG C of the Alloy plastic particle drying 4 hours of acquisition, adds in injection molding machine hopper, sets corresponding Shooting Technique, note
Plastic compression film is molded to obtain the standard batten of test.Test result is as shown in table 1.
1 ABS/PBT alloy properties of table
As shown in Table 1, the ABS/PBT alloy material poor compatibilities of bulking agent are not added, and notch impact strength is relatively low, adds in increase-volume
The compatibility of agent alloy product is improved, notch impact strength raising.As can be seen that the present invention prepare connect containing epoxy group
Graft copolymer compatibilization effect is better than common epoxies bulking agent on the market at present；Embodiment 1 is compared with comparative example 1,2, in phase
Under the conditions of near molecular weight and epoxy group content, the graft copolymer bulking agent containing epoxy group prepared by the present invention is than existing
The line style and the bulking agent of comb-type structure that technology obtains have better compatibilization effect.
Meanwhile be added to the ABS/PBT alloy molten indexes of the graft copolymer containing epoxy group that prepare of the present invention have compared with
Significantly decline, graft copolymer containing epoxy group and the carboxyl cross-linking reaction in PBT improve the molecular weight of PBT, this hair
The graft copolymer containing epoxy group of bright preparation also has the function of chain extender.
Claims (15)
1. a kind of graft copolymer containing epoxy group, which is characterized in that the graft copolymer is containing epoxy group and high score
A kind of polymer of sub- copolymer side chain, is made by following substance reaction：
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 30wt% containing epoxy group；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing epoxy group is 10000 ~ 100000, weight average molecular weight for 34000 ~
200000。
2. the graft copolymer containing epoxy group according to claim 1, which is characterized in that be made by following substance reaction：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing epoxy group；
The high molecular polymer C of 10wt% ~ 20wt% carbon-carbon double bonds.
3. the graft copolymer containing epoxy group according to claim 1, which is characterized in that the polyphosphazene polymer of carbon-carbon double bonds
It closes object C to be obtained by the reaction by the monomer E of polymer D and carbon-carbon double bonds, the polymer D chemical general formulas are：
Wherein R1For methyl, ethyl or butyl, R2For hydrogen atom or methyl, R3For methyl, ethyl, propyl, butyl, tertiary butyl or
Octyl group works as R2During for methyl, R1、R3It is different；M is 20 ~ 100 integer, and k is 1 ~ 99 integer, and n is 1 ~ 100 integer, q for 2 ~
12 integer；S is sulphur atom, and G is the group reacted with the monomer E of carbon-carbon double bonds, is in carboxyl, amino or hydroxyl
It is a kind of.
4. the graft copolymer containing epoxy group according to claim 3, which is characterized in that the high score of the carbon-carbon double bonds
Sub- polymer C number-average molecular weights are 4000 ~ 12000.
5. the graft copolymer containing epoxy group according to claim 3, which is characterized in that the monomer of the carbon-carbon double bonds
E carries epoxy group, amino, isocyanate group or acid chloride group.
6. the graft copolymer containing epoxy group according to claim 5, which is characterized in that the monomer of the carbon-carbon double bonds
E is acrylamide or Methacrylamide, glycidyl methacrylate or allyl glycidyl ether, acryloyl chloride or first
One kind in base acryloyl chloride, methylacryoyloxyethyl isocyanates and its derivative.
7. the graft copolymer containing epoxy group according to claim 3, which is characterized in that the polymer D and carbon containing carbon
The molar ratio of the monomer E of double bond is 1:0.8~1.3.
8. the graft copolymer containing epoxy group according to claim 1, which is characterized in that the monomer of the carbon-carbon double bonds
A for methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, methyl acrylate,
Ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, styrene, α-methylstyrene, α-ethyl styrene, acrylonitrile, first
It is one or more in base acrylonitrile and its derivative.
9. the graft copolymer containing epoxy group according to claim 1, which is characterized in that the insatiable hunger containing epoxy group
It is one or more in glycidyl methacrylate, allyl glycidyl ether and its derivative with monomer B.
10. the graft copolymer containing epoxy group according to claim 3, which is characterized in that the polymer D is by acrylic acid
One or more and chain-transferring agent in esters or methacrylate-based monomer causes free radical polymerization by initiator and is made；
The chain-transferring agent is one kind in the aliphatic mercaptan containing carboxyl, hydroxyl or amino；The initiator causes for azo
One kind in agent, peroxide initiator or redox initiator.
11. the graft copolymer containing epoxy group according to claim 1, which is characterized in that the connecing containing epoxy group
Graft copolymer by the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing epoxy group and carbon-carbon double bonds high molecular polymer
C is copolymerized by free radical polymerisation process.
12. the graft copolymer containing epoxy group according to claim 11, which is characterized in that the free radical polymerisation process
For one kind in bulk polymerization, polymerisation in solution, suspension polymerisation or emulsion polymerization.
13. the graft copolymer containing epoxy group according to claim 1, which is characterized in that the connecing containing epoxy group
Graft copolymer viscous state temperature is 110 DEG C ~ 200 DEG C.
14. the graft copolymer containing epoxy group according to claim 1, which is characterized in that the connecing containing epoxy group
Graft copolymer viscous state temperature is 140 DEG C ~ 180 DEG C.
15. the graft copolymer containing epoxy group described in any one of claim 1 ~ 14 as polymer blend bulking agent and
The application of the chain extender of polymer.
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| PCT/CN2017/112489 WO2018121138A1 (en) | 2016-12-27 | 2017-11-23 | Graft copolymer containing epoxy group and application thereof |
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|---|---|---|---|---|
| CN110615873A (en) * | 2019-09-03 | 2019-12-27 | 铨盛聚碳科技股份有限公司 | Comb-shaped epoxy group-containing compatilizer and preparation method thereof |
| CN113861636A (en) * | 2021-10-27 | 2021-12-31 | 佳易容聚合物(上海)有限公司 | High-stiffness high-toughness fully-degradable PBAT/PLA resin composition and preparation method thereof |
| CN114369213A (en) * | 2022-01-14 | 2022-04-19 | 河北明润复合材料科技有限公司 | PET tackifier, PET foam material and preparation method thereof |
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| CN113174014B (en) * | 2021-05-20 | 2022-09-02 | 传美讯电子科技（珠海）有限公司 | Acrylate comb dispersant, preparation method and application thereof, and organic pigment ink-jet color paste |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421154A (en) * | 2013-07-25 | 2013-12-04 | 杭州师范大学 | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof |
| CN104610515A (en) * | 2014-12-24 | 2015-05-13 | 杭州师范大学 | Reactive group-contained comb-type graft copolymer, and preparation method and application thereof |
| CN105778459A (en) * | 2016-03-15 | 2016-07-20 | 常州塑金高分子科技有限公司 | PC/ABS functional regenerated alloy for casing materials and production technology of PC/ABS functional regenerated alloy |
-
2016
- 2016-12-27 CN CN201611226765.2A patent/CN108239234B/en active Active
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421154A (en) * | 2013-07-25 | 2013-12-04 | 杭州师范大学 | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof |
| CN104610515A (en) * | 2014-12-24 | 2015-05-13 | 杭州师范大学 | Reactive group-contained comb-type graft copolymer, and preparation method and application thereof |
| CN105778459A (en) * | 2016-03-15 | 2016-07-20 | 常州塑金高分子科技有限公司 | PC/ABS functional regenerated alloy for casing materials and production technology of PC/ABS functional regenerated alloy |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615873A (en) * | 2019-09-03 | 2019-12-27 | 铨盛聚碳科技股份有限公司 | Comb-shaped epoxy group-containing compatilizer and preparation method thereof |
| CN113861636A (en) * | 2021-10-27 | 2021-12-31 | 佳易容聚合物(上海)有限公司 | High-stiffness high-toughness fully-degradable PBAT/PLA resin composition and preparation method thereof |
| CN114369213A (en) * | 2022-01-14 | 2022-04-19 | 河北明润复合材料科技有限公司 | PET tackifier, PET foam material and preparation method thereof |
| CN114369213B (en) * | 2022-01-14 | 2023-07-14 | 河北明润复合材料科技有限公司 | PET tackifier, PET foaming material and preparation method thereof |
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