CN108239234B - 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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- CN108239234B CN108239234B CN201611226765.2A CN201611226765A CN108239234B CN 108239234 B CN108239234 B CN 108239234B CN 201611226765 A CN201611226765 A CN 201611226765A CN 108239234 B CN108239234 B CN 108239234B
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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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- 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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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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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
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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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- 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
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- 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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- 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
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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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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- 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
Abstract
The present invention discloses a kind of graft copolymer containing epoxy group and its application.The graft copolymer is the quasi polymer containing epoxy group and high-molecular copolymer side chain, and mainly unsaturated monomer B, 5wt% by monomer A, 5wt% ~ 30wt% of 40wt% ~ 90wt% carbon-carbon double bonds containing epoxy group ~ 30wt% carbon-carbon double bonds high molecular polymer C are copolymerized by free radical polymerization.Preparation process are as follows: obtain high molecular polymer D first with free-radical polymerized, then utilize the high molecular polymer C of the reaction preparation carbon-carbon double bonds 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 used as the expanding material of polymer blend and the chain extender of polymer.
Description
Technical field
The present invention relates to the synthesis of graft copolymer and application fields, and in particular to a kind of acrylate containing epoxy group
Graft copolymer and its application.
Background technique
Expanding material refers to using means physically or chemically, and incompatible co-mixing system is promoted to be combined together, and then
To the auxiliary agent for stablizing co-mixing system.For polymer blend, due between each component in chemical structure, polarity, molecular weight
(viscosity) causes mutually to separate with the difference in crystallinity, leads to the poor performance of polymer blend.Therefore, expanding material is high level
The foundation stone of blending and modifying product.Especially in current raw material and modified materials market, the factory formula of enterprise and process flow
Come into the open mostly, transparence, the addition of expanding material then becomes the key point of material modification manufacturer and rival's differentiation.
For, containing the polymer blend of reactive group, usually using reactive compatibilizer in system.Common reaction
Type expanding material is mostly Graft copolymer, such as PP grafted maleic anhydride (102924661 B, CN 101519477 of Chinese patent CN
B), styrene-grafted maleic anhydride (102993350 B of Chinese patent CN), ABS grafted maleic anhydride etc..This kind of expanding material is more
The method squeezed out using frit reaction, the grafting functional group on polymer molecular chain obtain graft reaction type expanding material, raw
Production. art is simpler.Although this kind of expanding materials can solve the problems, such as polymer blend compatibility to a certain extent, due to work
Skill limitation, single variety, grafting rate is low, mostly acid anhydrides type expanding material.Compared with anhydride expanding material, epoxies expanding material and carboxylic
Base and hydroxyl have higher reactivity, have better compatibilization effect in polyester alloy.It is connect to obtain epoxy group
The expanding material of branch, 102492101 A of Chinese patent CN, which is disclosed, a kind of to be grafted to glycidyl methacrylate (GMA)
Method on ABS resin can obtain the graft with epoxy group using the technique of fusion-grafting, although method is simple,
Side reaction is more, reacts difficult to control, epoxy grafting rate highest only has 0.67%.Additive amount is larger in actual use, increase-volume efficiency
Low, therefore, the expanding material that fusion-grafting method obtains tends not to meet actual demand.
In order to realize effective control to expanding material structure and grafting rate, patent of invention of the E.I.Du Pont Company early in 1973
Ethylene-butyl acrylate-glycidyl methacrylate (PTW) ternary is just prepared using the method for copolymerization in US3723570
Copolymer compatibilizing agent.On this basis, 101851321 B of Chinese patent CN uses the technique of suspension polymerisation, and it is total to be prepared for ternary
Polymers expanding material styrene-acrylonitrile-glycidyl methacrylate (SAG) expanding material, can control ring by this method
The content of oxygen groups, obtains the expanding material 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 expanding material is especially suitable for ABS class alloy system.Compared with other expanding materials,
The expanding material can effectively improve the compatibility (102181122 A of CN) of ABS Yu polyethylene terephthalate (PET) alloy
With the thermal stability (104877326 A of CN) of polycarbonate and ABS alloy.
The structure of the above expanding material is mostly line style expanding material, in practical applications, the reactive group content of high grafting rate
Can be improved the compatibility with a wherein phase, but can only often rely on the winding of molecule interchain with another phase, active force compared with
It is weak.And by adjusting expanding material structure, while guaranteeing reactive group grafting rate, introduced and another phase on its main chain
The polymer segment of thermodynamic compatibility can effectively improve the winding and two alternate compatibilities of molecule interchain.Chinese patent
103421154 A of CN discloses a kind of comb-grafted copolymer and its preparation method and application containing reactive group.The patent
High grafting is obtained using free-radical polymerized method by introducing polyacrylate homopolymers segment on polymer lateral chain
The comb-shaped polymer of rate.Compared with the expanding material of commercialization, which can effectively improve the modulus of PET/ABS alloy, fracture
Elongation, yield strength and tensile strength etc. have higher better increase-volume efficiency (WY than the line style expanding material of identical grafting rate
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, expanding material 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 expanding material side chain has specific polarity and solubility simultaneously
Parameter also limits its application to a certain extent.
Summary of the invention
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 object of the invention is also to provide the graft copolymers containing epoxy group as polymer blend expanding material
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
One quasi polymer of chain, is made by following substance reaction:
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer B 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 be 10000 ~ 100000, weight average molecular weight be 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
Saturation monomer B reacts to obtain the graft copolymer containing epoxy group.As expanding material in use, the epoxy group of high grafting rate contains
The compatibility with a wherein phase can be improved in amount, 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 the selection and proportion of adjusting different monomers, it can be achieved that side chain strand flexibility
Control, but also the solubility parameter of adjustable side chain polymer segment preferably improve the phase of expanding material and another phase
Capacitive enhances two alternate binding forces.The height that graft copolymer prepared by the present invention containing epoxy group is obtained with the prior art connects
Branch rate line style is compared with the expanding material of comb-type structure, has better increase-volume effect in the case where close molecular weight and grafting rate
Fruit, can be used as expanding material and polymer chain extender uses.
The graft copolymer containing epoxy group, is made by following substance reaction:
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer B 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 reacted to obtain by polymer D with the monomer E of carbon-carbon double bonds, institute
State polymer D chemical general formula are as follows:
Wherein R1For methyl, ethyl or butyl, R2For hydrogen atom or methyl, R3For methyl, ethyl, propyl, butyl, tertiary fourth
Base or octyl, work as R2When for methyl, R1、R3It is different；The integer that m is 20 ~ 100, the integer that k is 1 ~ 99, the integer that n is 1 ~ 100, 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 carboxyl, amino or hydroxyl
One of.
Preferably, the high molecular polymer C number-average molecular weight of the carbon-carbon double bonds is 4000 ~ 12000.
The high molecular polymer C glass transition temperature of the carbon-carbon double bonds is 10 DEG C ~ 100 DEG C.
The monomer E of the carbon-carbon double bonds has epoxy group, amino, isocyanate group or acid chloride group.
Preferably, the monomer E of the carbon-carbon double bonds is that acrylamide or Methacrylamide, Glycidyl methacrylate are sweet
Grease or allyl glycidyl ether, acryloyl chloride or methacrylic chloride, methylacryoyloxyethyl isocyanates and its spread out
One of 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 be methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Isooctyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, styrene, Alpha-Methyl
One of styrene, α-ethyl styrene, acrylonitrile, methacrylonitrile and its derivative are a variety of.
The unsaturated monomer B containing epoxy group be glycidyl methacrylate, allyl glycidyl ether and
One of its derivative is a variety of.
The polymer D is by one of esters of acrylic acid or methacrylate-based monomer or a variety of leads to chain-transferring agent
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 of 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 of 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, pelletizer production；It is also possible to powder
The powder that broken mechanism is made.
The graft copolymer containing epoxy group can be used as the expanding material of polymer blend and the chain extender of polymer.
Compared with prior art, the invention has the following beneficial effects:
Graft copolymer prepared by the present invention containing epoxy group is used as expanding material, and the epoxy group of high grafting rate contains
The compatibility with a wherein phase can be improved in amount, and the copolymer for the polyacrylate that side chain introduces passes through different acrylate list
The control to side chain strand flexibility can be achieved in the selection of body and proportion, moreover it is possible to adjust the solubility ginseng of side chain polymer segment
Number preferably improves the compatibility of graft copolymer and another phase, enhances two alternate binding forces.The height obtained with the prior art
Grafting rate line style is compared with the expanding material of comb-type structure, is had in the case where similar molecular weight and epoxy group content more preferable
Compatibilization effect.Graft copolymer prepared by the present invention containing epoxy group can also be crosslinked with polymer to react, and improves
Polymer molecular weight plays chain extender；Compared with common linear polymer chain extender, what the present invention obtained contains epoxy group
Graft copolymer has higher molecular weight, and chain extension effect becomes apparent.
Detailed description of the invention
Fig. 1 is the infrared spectrum of the graft copolymer containing epoxy group prepared in embodiment 1.
Fig. 2 is the GPC spectrogram of the graft copolymer containing epoxy group prepared in embodiment 1.
Specific embodiment
Explanation is further expalined to the present invention combined with specific embodiments below, the description thereof is more specific and detailed, but
It cannot be construed as a limitation to the scope of the present invention, as long as the form using equivalent substitution or equivalent transformation is obtained
The technical solution obtained should all include within the scope of protection of the claims of the present invention.
In following embodiment, raw material used is commercial goods.
Test and characterizing method
(1) examination of infrared spectrum
Tabletting after potassium bromide after the graft copolymer containing epoxy group of acquisition and drying is milled, is placed on Fourier
Transform infrared spectrometer is tested.4000 ~ 400cm of scanning range-1, resolution ratio 4cm-1, scanning times 16 times.
(2) gel permeation chromatography (GPC) is tested
After the graft copolymer containing epoxy group of acquisition is dissolved with tetrahydrofuran, measured using gel permeation chromatograph
The retention time of polymer, detecting instrument are refraction index analyzer, and mobile phase is tetrahydrofuran, using monodisperse polystyrene
Relative molecular weight and its distribution of polymer are calculated as standard specimen.
(3) viscous state temperature test
By the graft copolymer containing epoxy group of acquisition after heating melting, the thin slice that thickness is about 2mm is made, and
Using the temperature strain curve of thermomechanical analyzer (TMA) test copolymer, copolymer is obtained according to temperature strain curve
Viscous state temperature.
Embodiment 1
Under nitrogen protection, by 80g methyl methacrylate, 20g ethyl acrylate, 1.5g chain-transferring agent mercaprol,
After 4.5g initiator azodiisobutyronitrile and 200g solvent toluene are mixed evenly, move to equipped with agitating paddle, condenser and temperature
It spends in the four-hole bottle of meter, is heated to 65 DEG C, after reacting 6h, obtain the toluene solution of the D containing polymer；Reaction system is down to room
0.01g hydroquinone of polymerization retarder, 0.04g catalyst n, the monomer E of N- dimethyl benzylamine and 2.1g carbon-carbon double bonds is added in temperature
Methacrylic chloride (polymer D is 1:1.2 with monomer E molar ratio), after reaction 8h is stirred at room temperature, after product revolving drying,
The high molecular polymer C of carbon-carbon double bonds is obtained, by the number-average molecular weight of the high molecular polymer C obtained known to GPC test
About 4200.
Under nitrogen protection, by 80g methyl methacrylate, 40g butyl acrylate, 20g glycidyl methacrylate,
High molecular polymer C, 4.5g azodiisobutyronitrile and 150g toluene of the carbon-carbon double bonds of the above-mentioned preparation of 10g are mixed evenly
Afterwards (the high molecular polymer C dosage of monomer A, monomer B and carbon-carbon double bonds be respectively 80.00wt%, 13.33wt% and
6.67wt%), it moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, is heated to 75 DEG C, after reacting 6h, product is revolved
Be evaporated it is dry after, obtain graft copolymer.By infrared spectroscopy 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, by 60g methyl methacrylate, 50g butyl acrylate, 1.5g chain-transferring agent mercaprol,
After 3.5g initiator azodiisobutyronitrile and 250g solvent xylene are mixed evenly, move to equipped with agitating paddle, condenser and
In the four-hole bottle of thermometer, 65 DEG C are heated to, after reacting 6h, obtains the xylene solution of the D containing polymer；Reaction system is down to
The monomer E metering system of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 2.1g carbon-carbon double bonds is added in room temperature
Acyl chlorides (polymer D is 1:1.2 with monomer E molar ratio) after reaction 5h is stirred at room temperature, after product revolving drying, obtains carbon containing
The high molecular polymer C of carbon double bond.Number-average molecular weight by the high molecular polymer C obtained known to GPC test is about 5100.
It is under nitrogen protection, 110g styrene, 20g ethyl acrylate, 16g glycidyl methacrylate, 54g is above-mentioned
After high molecular polymer C, 2.1g azodiisobutyronitrile and 300g butyl acetate of the carbon-carbon double bonds of preparation are mixed evenly
(the high molecular polymer C dosage 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 spectroscopy 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 connects containing epoxy group
Graft copolymer viscous state temperature is about 169 DEG C.
Embodiment 3
Under nitrogen protection, by 80g ethyl methacrylate, 40g butyl acrylate, 2g chain-transferring agent mercaptoethanol, 1.2g
After initiator azobisisoheptonitrile and 150g solvent ethyl acetate are mixed evenly, move to equipped with agitating paddle, condenser and temperature
It spends in the four-hole bottle of meter, is heated to 70 DEG C, after reacting 5h, obtain the ethyl acetate solution of the D containing polymer；Reaction system is down to
The monomer E metering system of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 5.0g carbon-carbon double bonds is added in room temperature
Sour isocyano group ethyl ester (polymer D is 1:1.25 with monomer E molar ratio), after reaction 10h is stirred at room temperature, rotates drying for product
Afterwards, the high molecular polymer C of carbon-carbon double bonds is obtained.The equal molecule of number by the high molecular polymer C obtained known to GPC test
Amount about 11900.
Under nitrogen protection, by 120g methyl methacrylate, 15g glycidyl methacrylate, 15g above-mentioned preparation
(monomer A, monomer after high molecular polymer C, 1.6g benzoyl peroxide and 150g butanone of carbon-carbon double bonds are mixed evenly
The high molecular polymer C dosage of B and carbon-carbon double bonds is respectively 80.00wt%, 10.00wt% and 10.00wt%), it moves 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 spectroscopy 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 is viscous
Fluidised form temperature is about 175 DEG C.
Embodiment 4
Under nitrogen protection, by 50g butyl methacrylate, 50g methyl acrylate, 2g chain-transferring agent thioacetic acid, 1.6g
After initiator azobisisoheptonitrile and 150g solvent acetic acid butyl ester are mixed evenly, move to equipped with agitating paddle, condenser and temperature
It spends in the four-hole bottle of meter, is heated to 70 DEG C, after reacting 5h, obtain the butyl acetate solution of the D containing polymer；It is down to room temperature, is added
The monomer E Glycidyl methacrylate of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 4.0g carbon-carbon double bonds is sweet
Grease (polymer D and monomer E molar ratio be 1:1.3), 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.Number-average molecular weight by the high molecular polymer C obtained known to GPC test
About 10700.
Under nitrogen protection, 10g acrylonitrile, 30g α-methylstyrene, 50g methyl methacrylate, 5g allyl are contracted
High molecular polymer C, 1.6g azodiisobutyronitrile and 100g toluene of the carbon-carbon double bonds of the above-mentioned preparation of water glycerin ether, 5g mix
After mixing evenly (the high molecular polymer C dosage of monomer A, monomer B and carbon-carbon double bonds be respectively 90.00wt%, 5.00wt% and
5.00wt%), it moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, is heated to 75 DEG C, after reacting 8h, product is revolved
Be evaporated it is dry after, obtain graft copolymer.By infrared spectroscopy 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, by 60g methyl methacrylate, 40g methyl acrylate, 2g chain-transferring agent thioacetic acid, 1.8g
After initiator azobisisoheptonitrile and 120g solvent xylene are mixed evenly, move to equipped with agitating paddle, condenser and temperature
In the four-hole bottle of meter, 70 DEG C are heated to, after reacting 5h, obtains the xylene solution of the D containing polymer；It is down to room temperature, 0.01g is added
The monomer E glycidyl methacrylate of hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 2.4g carbon-carbon double bonds
(polymer D and monomer E molar ratio be 1:0.8), 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 known to GPC test
11800。
Under nitrogen protection, by 70g methyl methacrylate, 30g butyl acrylate, 60g glycidyl methacrylate,
High molecular polymer C, 1.5g benzoyl peroxide and 300g toluene of the carbon-carbon double bonds of the above-mentioned preparation of 40g are mixed evenly
Afterwards (the high molecular polymer C dosage of monomer A, monomer B and carbon-carbon double bonds be respectively 50.00wt%, 30.00wt% and
20.00wt%), it moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, is heated to 85 DEG C, after reacting 8h, by product
After revolving is dry, graft copolymer is obtained.By infrared spectroscopy 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, by 115g ethyl methacrylate, 5g butyl acrylate, 4 g chain-transferring agent thioacetic acid, 2.8g
After initiator azo-bis-iso-dimethyl and 120g solvent acetic acid butyl ester are mixed evenly, move to equipped with agitating paddle, condensation
In the four-hole bottle of device and thermometer, 70 DEG C are heated to, after reacting 5h, obtains the butyl acetate solution of the D containing polymer；It is warming up to
130 DEG C, the monomer E of 0.02g hydroquinone of polymerization retarder, 0.04g catalyst 4-methyl hexamethylene diamine and 4.8 g carbon-carbon double bonds is added
Glycidyl methacrylate (polymer D is 1:0.8 with monomer E molar ratio), after being stirred to react 12h, product is rotated dry
After dry, the high molecular polymer C of carbon-carbon double bonds is obtained.Divided equally by the number of the high molecular polymer C obtained known to GPC test
Son amount about 9300.
Under nitrogen protection, by 130g styrene, 45g allyl glycidyl ether, 25g above-mentioned preparation carbon-carbon double bonds
(monomer A, monomer B and carbon containing carbon after high molecular polymer C, 1.8g azodiisobutyronitrile and 200g dimethylbenzene are mixed evenly
The high molecular polymer C dosage of double bond is respectively 65.00wt%, 22.50wt% and 12.50wt%), it moves 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
It is under nitrogen protection, 80g methyl methacrylate, 30g Isooctyl acrylate monomer, 2.4g sulfydryl lauric acid/dodecanoic acid, 1.8g is even
After nitrogen bis-isobutyronitrile and 150g butyl acetate are mixed evenly, the four-hole bottle equipped with agitating paddle, condenser and thermometer is moved to
In, 70 DEG C are heated to, after reacting 5h, obtains the butyl acetate solution of the D containing polymer；Be added 0.02g hydroquinone of polymerization retarder and
The monomer E dimethylamino-propyl Methacrylamide (polymer D is 1:1 with monomer E molar ratio) of 1.6g carbon-carbon double bonds, stirring
After reacting 8h, after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Pass through what is obtained known to GPC test
The number-average molecular weight of high molecular polymer C is about 10500.
Under nitrogen protection, by 100g methyl methacrylate, 50 Isooctyl acrylate monomers, 30g methyl propenoic acid glycidyl
High molecular polymer C, 1.5g benzoyl peroxide and 150g butyl acetate of the carbon-carbon double bonds of the above-mentioned preparation of ester, 20g mix
(the high molecular polymer C dosage of monomer A, monomer B and carbon-carbon double bonds are respectively 75.00wt%, 15.00wt% after mixing evenly
And 10.00wt%), it moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, is heated to 85 DEG C, after reacting 10h, will produce
After object revolving is dry, graft copolymer is obtained.By infrared spectroscopy 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 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 methacrylate, 60g methyl acrylate, 2.4g mercaptoethylmaine, 4.2g azo two
After isobutyl cyanide and 250g ethyl acetate are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, add
Heat after reacting 7h, obtains the ethyl acetate solution of the D containing polymer to 65 DEG C；It is down to room temperature, 0.02g polymerization inhibitor is added to benzene two
The monomer E isocyanatoethyl (polymer D is 1:1 with monomer E molar ratio) of phenol and 4.8g carbon-carbon double bonds, room temperature
After being stirred to react 8h, after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.It is known by GPC test
To the number-average molecular weight of high molecular polymer C be about 4500.
Under nitrogen protection, by 80g methyl methacrylate, 10g glycidyl methacrylate, 10g above-mentioned preparation
(monomer A, monomer after high molecular polymer C, 4.5g azodiisobutyronitrile and 200g toluene of carbon-carbon double bonds are mixed evenly
The high molecular polymer C dosage of B and carbon-carbon double bonds is respectively 80.00wt%, 10.00wt% and 10.00wt%), it moves 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 spectroscopy 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 is viscous
Fluidised form temperature is about 170 DEG C.
Embodiment 9
Under nitrogen protection, by 40g methyl methacrylate, 60g butyl acrylate, 1.2g mercaptoethylmaine, 2.1g azo two
After isobutyronitrile 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；0.02g hydroquinone of polymerization retarder and 2.0g carbon-carbon double bonds are added
Monomer E glycidyl methacrylate (polymer D and monomer E molar ratio be 1:0.9), after being stirred to react 6h, by product
After revolving is dry, the high molecular polymer C of carbon-carbon double bonds is obtained.Know obtained high molecular polymer C's by GPC test
Number-average molecular weight is about 7400.
Under nitrogen protection, by 65g styrene, 25g acrylonitrile, 5g allyl glycidyl ether, the above-mentioned preparation of 5g it is carbon containing
(monomer A, monomer B after high molecular polymer C, 1.5g azodiisobutyronitrile and 80g butyl acetate of carbon double bond are mixed evenly
High molecular polymer C dosage with carbon-carbon double bonds is respectively 90.00wt%, 5.00wt% and 5.00wt%), it moves 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 spectroscopy it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, gained connects 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, by 60g methyl methacrylate, 50g ethyl acrylate, 1.5g chain-transferring agent mercaprol,
After 3.5g initiator azodiisobutyronitrile and 250g solvent toluene are mixed evenly, move to equipped with agitating paddle, condenser and temperature
It spends in the four-hole bottle of meter, is heated to 65 DEG C, after reacting 6h, obtain the toluene solution of the D containing polymer；Reaction system is down to room
0.01g hydroquinone of polymerization retarder, 0.02g catalyst n, the monomer E of N- dimethyl benzylamine and 2.1g carbon-carbon double bonds is added in temperature
Methacrylic chloride (polymer D is 1:1.2 with monomer E molar ratio), after reaction 5h is stirred at room temperature, after product revolving drying,
The high molecular polymer C of carbon-carbon double bonds is obtained, by the number-average molecular weight of the high molecular polymer C obtained known to GPC test
About 5100.
By 80g styrene, 18g butyl acrylate, 10g glycidyl methacrylate, the above-mentioned preparation of 12g carbon containing carbon
The high molecular polymer C of double bond, 2.4 g anion emulsifier lauryl sodium sulfate, 1.2g nonionic emulsifier polyoxyethylene
High-speed mixer high-speed stirred 15min is used after octyl phenol ether, 0.75g initiator potassium persulfate and the mixing of 175g distilled water,
Obtaining pre-emulsion, (the high molecular polymer C dosage 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 the CaCl that 10 ml concentration are 5% is added2Aqueous solution, after demulsification precipitates
Product is washed repeatedly with distilled water, is crushed after then drying, obtains graft copolymer.By infrared spectroscopy 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 methacrylate, 60g methyl acrylate, 2.4g mercaptoethylmaine, 4.2g azo two
After isobutyl cyanide and 250g ethyl acetate are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, add
Heat after reacting 7h, is down to room temperature, obtains the ethyl acetate solution of the D containing polymer to 65 DEG C；0.02g polymerization inhibitor is added to benzene two
The monomer E isocyanatoethyl (polymer D is 1:1 with monomer E molar ratio) of phenol and 4.8g carbon-carbon double bonds, room temperature
After being stirred to react 8h, after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.It is known by GPC test
To the number-average molecular weight of high molecular polymer C be 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 methacrylate, 10g allyl glycidyl ether, 1.5g initiator (NH4)2S2O8-FeSO4、
The high molecular polymer C of the carbon-carbon double bonds of the above-mentioned preparation of the 30g (height of monomer A, monomer B and carbon-carbon double bonds after mixing
Molecularly Imprinted Polymer C dosage is respectively 66.67wt%, 8.33wt% and 25.00wt%), it is added 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, obtain graft copolymer after dry.By infrared spectroscopy 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
Under nitrogen protection, by 100g methyl methacrylate, 30g butyl acrylate, 20g methyl propenoic acid glycidyl
After ester, 2.1g initiator azodiisobutyronitrile and 200g solvent toluene are mixed evenly, move to equipped with agitating paddle, condenser and
In the four-hole bottle of thermometer, 75 DEG C are heated to, after reacting 6h, is down to room temperature, after product revolving drying, obtains line style copolymerization
Object.By infrared spectroscopy it is found that obtained linear copolymers contain epoxy group；It is tested by GPC, line of the gained containing epoxy group
Type copolymer number-average molecular weight is about 17920, weight average molecular weight 51800.
Comparative example 2
It is under nitrogen protection, 100g methyl methacrylate, 3.2g chain-transferring agent thioacetic acid, 3g initiator azo two is different
It after butyronitrile and 200g solvent toluene are mixed evenly, moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, heats
To 65 DEG C, after reacting 6h, it is down to room temperature, 0.01g hydroquinone of polymerization retarder, 0.04g catalyst of triethylamine and 5g methyl-prop is added
Olefin(e) acid ethylene oxidic ester after 100 DEG C are stirred to react 10h, after product revolving drying, obtains the high molecular polymerization of carbon-carbon double bonds
Object C, the number-average molecular weight by the high molecular polymer C obtained known to GPC test is about 4100.
Under nitrogen protection, by 120g methyl methacrylate, 20g glycidyl methacrylate, 10g above-mentioned preparation
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 spectroscopy 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 expanding material
It is compared applied to preparation ABS and polybutylene terephthalate (PBT) (PBT) alloy, and with Commercial epoxy class expanding material.Wherein
63 parts of ABS in ABS/PBT alloy formula, 35 parts of PBT, 2 parts of expanding material；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 it is water cooled by sink, drying after feeding pelleter pelletizing obtain ABS/
Injection molding machine hopper is added in 80 DEG C of the Alloy plastic particle drying 4 hours of acquisition by PBT alloy, sets corresponding Shooting Technique, note
Plastic compression film forms to obtain the standard batten of test.Test result is as shown in table 1.
1 ABS/PBT alloy property of table
As shown in Table 1, the ABS/PBT alloy material poor compatibility of expanding material is not added, and notch impact strength is lower, is added
The compatibility of expanding material alloy product is improved, and notch impact strength increases.As can be seen that prepared by the present invention contain epoxy group
Group's graft copolymer compatibilization effect is better than common epoxies expanding material on the market at present；Embodiment 1 compared with comparative example 1,2,
Under the conditions of similar molecular weight and epoxy group content, the graft copolymer expanding material ratio prepared by the present invention containing epoxy group
The expanding material of line style and comb-type structure that the prior art obtains has better compatibilization effect.
Meanwhile the ABS/PBT alloy molten index for being added to the graft copolymer prepared by the present invention containing epoxy group have compared with
Carboxyl cross-linking reaction in a sharp decline, graft copolymer containing epoxy group and PBT, improves the molecular weight of PBT, this hair
The graft copolymer containing epoxy group of bright preparation also has the function of chain extender.
Claims (14)
1. a kind of graft copolymer containing epoxy group, which is characterized in that the graft copolymer is containing epoxy group and high score
One quasi polymer of sub- copolymer side chain, is made by following substance reaction:
The monomer A of 40wt%~90wt% carbon-carbon double bonds；
Unsaturated monomer B 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 be 10000~100000, weight average molecular weight be 34000~
200000；
The high molecular polymer C of carbon-carbon double bonds is reacted to obtain by polymer D with the monomer E of carbon-carbon double bonds, the polymer D
Chemical general formula are as follows:
Wherein R1For methyl, ethyl or butyl, R2For hydrogen atom or methyl, R3For methyl, ethyl, propyl, butyl, tert-butyl or
Octyl works as R2When for methyl, R1、R3It is different；The integer that m is 20~100, the integer that k is 1~99, the integer that n is 1~100, 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 carboxyl, amino or hydroxyl
One of base.
2. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that be made by following substance reaction:
The monomer A of 60wt%~85wt% carbon-carbon double bonds；
Unsaturated monomer B of the 5wt%~20wt% containing epoxy group；
The high molecular polymer C of 10wt%~20wt% carbon-carbon double bonds.
3. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the high score of the carbon-carbon double bonds
Sub- polymer C number-average molecular weight is 4000~12000.
4. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the monomer of the carbon-carbon double bonds
E has epoxy group, amino, isocyanate group or acid chloride group.
5. according to claim 4 containing the graft copolymer of epoxy group, 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 of base acryloyl chloride, methylacryoyloxyethyl isocyanates and its derivative.
6. according to claim 1 containing the graft copolymer of epoxy group, 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.
7. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the monomer of the carbon-carbon double bonds
A be 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
One of base acrylonitrile and its derivative are a variety of.
8. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the insatiable hunger containing epoxy group
It with monomer B is one of glycidyl methacrylate, allyl glycidyl ether and its derivative or a variety of.
9. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the polymer D is by acrylic acid
A variety of and chain-transferring agent in esters or methacrylate-based monomer causes free radical polymerization by initiator and is made；The chain
Transfer agent is one of the aliphatic mercaptan containing carboxyl, hydroxyl or amino；The initiator is azo-initiator, peroxide
One of compound initiator or redox initiator.
10. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the connecing containing epoxy group
Graft copolymer is by the monomer A of carbon-carbon double bonds, the high molecular polymer of the unsaturated monomer B containing epoxy group and carbon-carbon double bonds
C is copolymerized by free radical polymerisation process.
11. according to claim 10 containing the graft copolymer of epoxy group, which is characterized in that the free radical polymerisation process
For one of bulk polymerization, polymerisation in solution, suspension polymerisation or emulsion polymerization.
12. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the connecing containing epoxy group
Graft copolymer viscous state temperature is 110 DEG C~200 DEG C.
13. according to claim 1 containing the graft copolymer of epoxy group, which is characterized in that the connecing containing epoxy group
Graft copolymer viscous state temperature is 140 DEG C~180 DEG C.
14. graft copolymer described in any one of claim 1~13 containing epoxy group as polymer blend expanding material with
And the application of the chain extender of polymer.
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