CN108239241A - A kind of graft copolymer and its application containing isocyanate groups - Google Patents
A kind of graft copolymer and its application containing isocyanate groups Download PDFInfo
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- CN108239241A CN108239241A CN201611226763.3A CN201611226763A CN108239241A CN 108239241 A CN108239241 A CN 108239241A CN 201611226763 A CN201611226763 A CN 201611226763A CN 108239241 A CN108239241 A CN 108239241A
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- graft copolymer
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- isocyanate groups
- containing isocyanate
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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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- 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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- 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
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- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
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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
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Abstract
The present invention discloses a kind of graft copolymer containing isocyanate groups and its application.The graft copolymer is a kind of polymer containing isocyanate groups 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 isocyanate groups ~ 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 isocyanate groups after dry devolatilization.Graft copolymer of the present invention containing isocyanate groups 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 propylene containing isocyanate groups
Acid esters 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 alloy compatibility to a certain extent, by
It is limited in technique, single varieties, grafting rate is low, and side reaction is more, and reaction is difficult to control.Additive amount is larger in actual use, increase-volume
Efficiency is low, and 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 can be up to 10%.Due to containing in system
Styrene and acrylonitrile unit, therefore the bulking agent is especially suitable for ABS class alloy systems.Compared with other bulking agents, the increasing
ABS and polyethylene terephthalate can be effectively improved by holding agent（PET）The compatibility of alloy（CN 102181122 A）With it is poly-
The thermal stability of carbonic ester and ABS alloy（CN 104877326 A）.
The structure of more than bulking agent is mostly linear copolymers bulking agent, in practical applications, the reactive base of high grafting rate
Mass contg can improve the compatibility with a wherein phase, but the winding of molecule interchain can only be often relied on another phase, make
It is firmly weaker.And by adjusting bulking agent structure, while reactive group grafting rate is ensured, introduced on its main chain and another
The polymer segment of one phase thermodynamic compatibility can effectively improve winding and the two alternate compatibilities of molecule interchain.In
103421154 A of state patent CN disclose a kind of comb-grafted copolymer containing reactive group and its preparation method and application.
The patent, using free-radical polymerized method, is obtained by introducing polyacrylate homopolymers segment on polymer lateral chain
The comb-shaped polymer of high grafting rate.Compared with the bulking agent of commercialization, which can effectively improve the mould of PET/ABS alloys
Amount, elongation at break, yield strength and tensile strength etc. have the better increase-volume of higher than the line style bulking agent of identical grafting rate
Efficiency（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 isocyanate groups.
The present invention also aims to provide the graft copolymer containing isocyanate groups as polymer blend to increase
Hold 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 isocyanate groups, the graft copolymer are containing isocyanate groups and polymer copolymerization
A kind of polymer of object 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 isocyanate groups；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing isocyanate groups is 11000 ~ 73000, weight average molecular weight for 36000 ~
144000。
The present invention utilizes the high molecular polymer C of carbon-carbon double bonds and the monomer A of carbon-carbon double bonds, containing isocyanate groups
Unsaturated monomer B the graft copolymer containing isocyanate groups is obtained by the reaction.As bulking agent in use, isocyanate groups
The compatibility with a wherein phase can be improved, and the high molecular polymer C of carbon-carbon double bonds is as graft copolymer in the present invention
Side chain, introduce copolymer, by adjust different monomers selection and proportioning, it can be achieved that control to side chain strand compliance
System, but also the solubility parameter of side chain polymer segment can be adjusted, it is compatible with another phase preferably to improve bulking agent
Property, enhance two alternate binding forces.The line that graft copolymer containing isocyanate groups prepared by the present invention is obtained with the prior art
Type is compared with the bulking agent of comb-type structure, is had better compatibilization effect under close molecular mass regimes, can be used as blending polymerization
The bulking agent and polymer chain extender of object alloy use.
The graft copolymer containing isocyanate groups, is made by following substance reaction：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing isocyanate groups；
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 isocyanate groups is isocyanatoethyl, 3- isopropyls-dimethyl
It is one or more in benzyl isocyanate ester, isocyanates ethyl acrylate and 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 isocyanate groups by the monomer A of carbon-carbon double bonds, containing isocyanate groups not
Saturation monomer B and the high molecular polymer C of carbon-carbon double bonds are copolymerized by free radical polymerisation process.
The free radical polymerisation process is polymerisation in solution.
The graft copolymer viscous state temperature containing isocyanate groups is 110 DEG C ~ 200 DEG C.
Preferably, the graft copolymer viscous state temperature containing isocyanate groups is 140 DEG C ~ 180 DEG C.
The graft copolymer containing isocyanate groups can be by the particle of pelleter, comminutor making；It can also
It is the powder that pulverizer makes.
The graft copolymer containing isocyanate groups can be as the expansion of the bulking agent and polymer of polymer blend
Chain agent.
Compared with prior art, the present invention has the advantages that：
Graft copolymer containing isocyanate groups prepared by the present invention is used as bulking agent, the isocyanate groups of high-content
The compatibility with a wherein phase can be improved, the copolymer for the polyacrylate that side chain introduces passes through different acrylate monomer
Selection and proportioning control to side chain strand compliance can be achieved, moreover it is possible to adjust the solubility ginseng of side chain polymer segment
Number preferably improves graft copolymer and the compatibility of another phase, enhances two alternate binding forces.Prepared by the present invention contains isocyanide
The graft copolymer of acid esters group can also be crosslinked with polymer to react, and improves polymer molecular weight, plays chain extender；
Compared with common linear polymer chain extender, the graft copolymer that the present invention obtains has higher molecular weight, chain extension effect
It becomes apparent.
Description of the drawings
Fig. 1 is the GPC spectrograms of the graft copolymer containing isocyanate groups 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）Gel permeation chromatography（GPC）Test
After the graft copolymer containing isocyanate groups 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
The relative molecular weight of polymer and its distribution are calculated as standard specimen.
（Two）Viscous state temperature test
By the graft copolymer containing isocyanate groups of acquisition after heating melts, the thin slice that thickness is about 2mm is made, and
Using thermomechanical analyzer（TMA）The temperature strain curve of copolymer is tested, copolymer is obtained according to temperature strain curve
Viscous 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 isocyanatoethyls,
High molecular polymer C, 4.5g azodiisobutyronitrile and 210g dimethylbenzene of the carbon-carbon double bonds of the above-mentioned preparations of 10g are mixed equal
After even（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 the graft copolymer containing isocyanate groups.It is tested by GPC, as shown in Figure 1, gained contains isocyanates
The graft copolymer number-average molecular weight of group is about 14746, weight average molecular weight 47114；Gained connecing containing isocyanate groups
Graft copolymer viscous state temperature is about 153 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 ethyl acetates are mixed evenly, move to equipped with agitating paddle, condenser and temperature
In the four-hole bottle of meter, 65 DEG C are heated to, after reacting 6h, obtains the ethyl acetate solution of the D containing polymer；Reaction system is down to room
Temperature adds in the monomer E metering systems of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine 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 5310.
Under nitrogen protection, by 100g styrene, 30g ethyl acrylates, 20g isocyanates ethyl acrylate, the above-mentioned systems of 50g
After high molecular polymer C, 2.1g azodiisobutyronitrile and 300g butyl acetates of standby carbon-carbon double bonds are mixed evenly（It is single
The high molecular polymer C dosages of body A, monomer B and carbon-carbon double bonds are respectively 65.00wt%, 10.00wt% and 25.00wt%）, move
Into the four-hole bottle equipped with agitating paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, is obtained
To the graft copolymer containing isocyanate groups.It is tested by GPC, graft copolymer number of the gained containing isocyanate groups is divided equally
Son amount about 28410, weight average molecular weight 72100；Graft copolymer viscous state temperature of the gained containing isocyanate groups be about
170℃。
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 isocyanatoethyls, 15g above-mentioned preparations
After high molecular polymer C, 1.2g benzoyl peroxide and 150g 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, 80 DEG C are heated to, after reacting 8h, after product revolving drying, is obtained containing isocyanide
The graft copolymer of acid esters group.It is tested by GPC, graft copolymer number-average molecular weight of the gained containing isocyanate groups is about
58100, weight average molecular weight 117200；Graft copolymer viscous state temperature of the gained containing isocyanate groups is about 176 DEG C.
Embodiment 4
Under nitrogen protection, 60g butyl methacrylates, 40g methyl acrylates, 2g chain-transferring agents thioacetic acid, 1.8g 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
9900。
Under nitrogen protection, by 10g acrylonitrile, 30g α-methylstyrenes, 50g methyl methacrylates, 5g isocyanates
High molecular polymer C, 2.1g azodiisobutyronitrile of the carbon-carbon double bonds of the above-mentioned preparation of ethyl acrylate, 5g and 100g dimethylbenzene
After being mixed 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, react 8h
Afterwards, by after product revolving drying, the graft copolymer containing isocyanate groups is obtained.It is tested by GPC, gained contains isocyanates
The graft copolymer number-average molecular weight of group is about 24800, weight average molecular weight 68600；Gained connecing containing isocyanate groups
Graft copolymer viscous state temperature is about 180 DEG C.
Embodiment 5
Under nitrogen protection, 70g methyl methacrylates, 30g ethyl acrylates, 2g chain-transferring agents thioacetic acid, 2.1g 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 11300.
Nitrogen protection under, by 70g methyl methacrylates, 30g butyl acrylates, 60g isocyanatoethyls,
High molecular polymer C, 1.2g 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, the graft copolymer containing isocyanate groups is obtained.It is tested by GPC, gained connecing containing isocyanate groups
Graft copolymer number-average molecular weight is about 39800, weight average molecular weight 85600；Graft copolymer of the gained containing isocyanate groups
Viscous state temperature is about 155 DEG C.
Embodiment 6
Under nitrogen protection, 115g ethyl methacrylate, 5g butyl acrylates, 4g chain-transferring agents thioacetic acid, 2.4g 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 10900.
Under nitrogen protection, by 130g styrene, 45g 3- isopropyls-dimethyl benzyl isocyanate, 25g above-mentioned preparations
After high molecular polymer C, 1.8g azodiisobutyronitrile and 200g dimethylbenzene of carbon-carbon double bonds are mixed evenly（Monomer A, list
The high molecular polymer C dosages of body B and carbon-carbon double bonds are respectively 65.00wt%, 22.50wt% and 12.50wt%）, move to and be equipped with
In the four-hole bottle of agitating paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, is obtained containing different
The graft copolymer of cyanate group.It is tested by GPC, graft copolymer number-average molecular weight of the gained containing isocyanate groups is about
It is 34300, weight average molecular weight 74100；Graft copolymer viscous state temperature of the gained containing isocyanate groups is about 159 DEG C.
Embodiment 7
Under nitrogen protection, by 80g methyl methacrylates, 40g Isooctyl acrylate monomers, 2.4g sulfydryls lauric acid/dodecanoic acid, 2.1g 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 10900.
Nitrogen protection under, by 100g methyl methacrylates, 50 Isooctyl acrylate monomers, 30g isocyanates ethyl acrylate,
High molecular polymer C, 1.2g benzoyl peroxide and 150g butyl acetates of the carbon-carbon double bonds of the above-mentioned preparations of 20g are mixed
After uniformly（The high molecular polymer C dosages of monomer A, monomer B and carbon-carbon double bonds be 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, by product
After revolving is dry, the graft copolymer containing isocyanate groups is obtained.It is tested by GPC, gained connecing containing isocyanate groups
Graft copolymer number-average molecular weight is about 73100, weight average molecular weight 143800；Graft copolymer of the gained containing isocyanate groups
Viscous state temperature is about 115 DEG C.
Embodiment 8
Under nitrogen protection, by 50g methyl methacrylates, 50g methyl acrylates, 2.4g mercaptoethylmaines, 4.4g azo diisoamyls
After nitrile and 280g 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 4300.
Under nitrogen protection, by 80g methyl methacrylates, 10g isocyanatoethyls, 10g above-mentioned preparations
After high molecular polymer C, 4.5g azodiisobutyronitrile and 250g 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, is obtained containing isocyanide
The graft copolymer of acid esters group.It is tested by GPC, graft copolymer number-average molecular weight of the gained containing isocyanate groups is about
11300, weight average molecular weight 36200；Graft copolymer viscous state temperature of the gained containing isocyanate groups is about 167 DEG C.
Embodiment 9
Under nitrogen protection, by 45g methyl methacrylates, 55g butyl acrylates, 1.2g mercaptoethylmaines, two isobutyl of 1.8g 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 8700.
Under nitrogen protection, by 65g styrene, 20g acrylonitrile, 25g isocyanates ethyl acrylate, 10g above-mentioned preparations
After high molecular polymer C, 1.2g azodiisobutyronitrile and 80g butyl acetates of carbon-carbon double bonds are mixed evenly（Monomer A,
The high molecular polymer C dosages of monomer B and carbon-carbon double bonds are respectively 70.84wt%, 20.83wt% and 8.33wt%）, move to dress
In the four-hole bottle for having agitating paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, is contained
The graft copolymer of isocyanate groups.It is tested by GPC, graft copolymer number-average molecular weight of the gained containing isocyanate groups
About 36700, weight average molecular weight 88600；Graft copolymer viscous state temperature of the gained containing isocyanate groups is about 184
℃。
Comparative example 1
Nitrogen protection under, by 100g methyl methacrylates, 30g butyl acrylates, 20g isocyanatoethyls,
After 2.4g initiator azodiisobutyronitriles and 250g 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 containing isocyanate group
The linear copolymers of group.It is tested by GPC, linear copolymers number-average molecular weight of the gained containing isocyanate groups is about 14600,
Weight average molecular weight is 46100.
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 isocyanatoethyls, 10g above-mentioned preparations
After high molecular polymer C, 2.4g 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, is obtained containing isocyanide
The comb-grafted copolymer of acid esters group.It is tested by GPC, comb-grafted copolymer number of the gained containing isocyanate groups is divided equally
Son amount about 14380, weight average molecular weight 47460.
Performance test
Using the graft copolymer containing isocyanate groups obtained in comparative example 1, comparative example 2 and embodiment 1-9 as bulking agent
Applied to preparation ABS and polybutylene terephthalate (PBT)（PBT）Alloy, and compared with commercially available bulking agent.Wherein ABS/PBT is closed
63 parts of ABS in gold 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 isocyanates prepared by the present invention connects
Graft copolymer compatibilization effect is better than common bulking agent on the market at present；Embodiment 1 is compared with comparative example 1,2, at similar point
Under conditions of son amount and isocyanate content, the graft copolymer bulking agent ratio containing isocyanate groups of the invention prepared
The line style and the bulking agent of comb-type structure that the prior art obtains have better compatibilization effect.
In addition, it is added to the ABS/PBT alloy molten indexes of the graft copolymer containing isocyanate groups prepared by the present invention
There is decline by a relatively large margin, the hydroxyl reaction crosslinking in graft copolymer and PBT containing isocyanate groups improves PBT's
Molecular weight, graft copolymer containing isocyanate groups prepared by the present invention also have the function of chain extender.
Claims (15)
1. a kind of graft copolymer containing isocyanate groups, which is characterized in that the graft copolymer is containing isocyanate group
Group and a kind of polymer of high-molecular copolymer side chain, are made by following substance reaction：
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 30wt% containing isocyanate groups；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing isocyanate groups is 11000 ~ 73000, weight average molecular weight for 36000 ~
144000。
2. the graft copolymer containing isocyanate groups according to claim 1, which is characterized in that by following substance reaction system
：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing isocyanate groups；
The high molecular polymer C of 10wt% ~ 20wt% carbon-carbon double bonds.
3. the graft copolymer containing isocyanate groups according to claim 1, which is characterized in that the high score of carbon-carbon double bonds
Sub- polymer C is obtained by the reaction by the monomer E of polymer D and carbon-carbon double bonds, and 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 isocyanate groups according to claim 3, which is characterized in that the carbon-carbon double bonds
High molecular polymer C number-average molecular weights are 4000 ~ 12000.
5. the graft copolymer containing isocyanate groups according to claim 3, which is characterized in that the carbon-carbon double bonds
Monomer E carries epoxy group, amino, isocyanate group or acid chloride group.
6. the graft copolymer containing isocyanate groups according to claim 5, which is characterized in that the carbon-carbon double bonds
Monomer E is acrylamide or Methacrylamide, glycidyl methacrylate or allyl glycidyl ether, acryloyl chloride
Or one kind in methacrylic chloride, methylacryoyloxyethyl isocyanates and its derivative.
7. the graft copolymer containing isocyanate groups according to claim 3, which is characterized in that the polymer D is with containing
The molar ratio of the monomer E of carbon-carbon double bond is 1:0.8~1.3.
8. the graft copolymer containing isocyanate groups according to claim 1, which is characterized in that the carbon-carbon double bonds
Monomer A is methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, acrylic acid first
Ester, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, styrene, α-methylstyrene, α-ethyl styrene, propylene
It is one or more in nitrile, methacrylonitrile and its derivative.
9. the graft copolymer containing isocyanate groups according to claim 1, which is characterized in that described to contain isocyanate group
The unsaturated monomer B of group is isocyanatoethyl, 3- isopropyls-dimethyl benzyl isocyanate, isocyanates third
It is one or more in olefin(e) acid ethyl ester and its derivative.
10. the graft copolymer containing isocyanate groups according to claim 3, which is characterized in that the polymer D is by third
One or more and chain-transferring agent in olefin(e) acid esters or methacrylate-based monomer causes free radical polymerization by initiator
It is made；The chain-transferring agent is one kind in the aliphatic mercaptan containing carboxyl, hydroxyl or amino；The initiator is azo
One kind in initiator, peroxide initiator or redox initiator.
11. the graft copolymer containing isocyanate groups according to claim 1, which is characterized in that described to contain isocyanates
The graft copolymer of group is by the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing isocyanate groups and carbon-carbon double bonds
High molecular polymer C is copolymerized by free radical polymerisation process.
12. the graft copolymer containing isocyanate groups according to claim 11, which is characterized in that the free radical polymerization
Method is polymerisation in solution.
13. the graft copolymer containing isocyanate groups according to claim 1, which is characterized in that described to contain isocyanates
The graft copolymer viscous state temperature of group is 110 DEG C ~ 200 DEG C.
14. the graft copolymer containing isocyanate groups according to claim 1, which is characterized in that described to contain isocyanates
The graft copolymer viscous state temperature of group is 140 DEG C ~ 180 DEG C.
15. bulking agent of the graft copolymer containing isocyanate groups as polymer blend described in any one of claim 1 ~ 14
And the application of the chain extender of polymer.
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| CN201611226763.3A CN108239241B (en) | 2016-12-27 | 2016-12-27 | Graft copolymer containing isocyanate group and application thereof |
| PCT/CN2017/112491 WO2018121140A1 (en) | 2016-12-27 | 2017-11-23 | Graft copolymer containing isocyanate group and application thereof |
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| 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 |
| CN105924619A (en) * | 2016-05-16 | 2016-09-07 | 常州大学 | Preparation method of compatilizer based on poly(styrene-co-acrylonitrile) |
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| JP2001106746A (en) * | 1999-10-12 | 2001-04-17 | Sekisui Chem Co Ltd | Modifier for polyolefin-based resin, polyolefin-based composition, and its molded product |
| JP4056423B2 (en) * | 2002-08-30 | 2008-03-05 | 三井化学株式会社 | Polyolefin macromonomer and process for producing the same |
| JP2005307097A (en) * | 2004-04-26 | 2005-11-04 | Kaneka Corp | Macromonomer |
| CN104031214B (en) * | 2014-06-23 | 2016-06-29 | 浙江工业大学 | A kind of St/MAH-g-MMA graft copolymer and its preparation method and application |
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| 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 |
| CN105924619A (en) * | 2016-05-16 | 2016-09-07 | 常州大学 | Preparation method of compatilizer based on poly(styrene-co-acrylonitrile) |
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| CN114015388A (en) * | 2021-12-20 | 2022-02-08 | 苏州赛伍应用技术股份有限公司 | Hydroxyl-containing viscose reducing agent composition and preparation method and application thereof |
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