CN108440725A - A kind of graft copolymer and its preparation method and application containing epoxy group - Google Patents
A kind of graft copolymer and its preparation method and application containing epoxy group Download PDFInfo
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- CN108440725A CN108440725A CN201810144836.7A CN201810144836A CN108440725A CN 108440725 A CN108440725 A CN 108440725A CN 201810144836 A CN201810144836 A CN 201810144836A CN 108440725 A CN108440725 A CN 108440725A
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- epoxy group
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- graft copolymer
- containing epoxy
- double bonds
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/044—Polymers of aromatic monomers as defined in group C08F12/00
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Abstract
The present invention discloses a kind of graft copolymer and its preparation method and application containing epoxy group.Graft copolymer is a kind of polymer of the side chain containing epoxy group and polystyrene and its derivative segment, is copolymerized by free radical polymerization by the high molecular polymer C of monomer A, 5wt% ~ 30wt% of 40wt% ~ 90wt% carbon-carbon double bonds unsaturated monomer B, 5wt% containing epoxy group ~ 30wt% carbon-carbon double bonds.Graft copolymer containing epoxy group prepared by the present invention can improve the intensity of polyphenylene oxide or styrene-based polymer and polyester alloy, the epoxy group content of high-content can improve the binding force with polyester, and the polystyrene and its derivative segment that side chain introduces can improve the binding force with another phase polyphenylene oxide or polystyrene based polymers.Compared with the graft copolymer of high grafting rate line style and comb-type structure that the prior art obtains, the intensity of polyphenylene oxide or styrene-based polymer and polyester alloy can be preferably improved in the case of similar molecular weight and epoxy group content.
Description
Technical field
The present invention relates to the synthesis of graft copolymer and application fields, and in particular to a kind of graft copolymerization containing epoxy group
Object and its preparation method and application.
Background technology
Polyphenylene oxide（PPE）With rigidity is big, heat resistance is high, fire retardant, water resistance and wearability is good and excellent electrical properties etc.
Advantage is widely used in the fields such as electric, auto industry and mechanical chemical industry.Pure PPE material have melt fluidity compared with
Difference and the high disadvantage of price, by with high impact polystyrene（HIPS）Blending can overcome these disadvantages, obtain function admirable
Modified polyphenyl ether product.Nevertheless, MODIFIED PP E solvent resistances are poor, its application is limited to a certain extent.Gather to benzene two
Formic acid butanediol ester（PBT）MODIFIED PP E and PBT blending and modifyings can be improved into the resistance to of PPE with excellent solvent resistance
Solvent nature.But after PPE is simply blended with PBT, the intensity of alloy can decline, and be unsatisfactory for practical application request.Therefore
It must be added to third component and improve its intensity.
The intensity of alloy, Chinese patent CN can be improved by adding some graft copolymers containing reactive group
102746468 A have found acrylic acid-grafted ethylene-octene block copolymer（OBC-g-AA）Addition can improve it is poly- to benzene two
Formic acid glycol ester（PET）With ethylene-octene block copolymer（OBC）The tensile strength and elongation at break of alloy.It is Chinese special
102020785 A of sharp CN are prepared for the PPE graft copolymers containing differential responses group using the method for fusion-grafting, and
It is applied to and prepares PPE and polyamide（PA）Alloy.The result shows that being added to the graft copolymers of PPE containing reactive group
Tensile strength, bending strength and the elongation at break of PPE/PA alloys are improved.This quasi-graft copolymer mostly uses melting
The method of reactive extrursion, the grafting functional group on polymer molecular chain, production technology is simpler, but since technique limits,
Single varieties, grafting rate are low.Additive amount is larger in actual use, and efficiency is low, and therefore, the grafting that fusion-grafting method obtains is total
Polymers tends not to meet actual demand.
In order to realize that effective control to graft copolymer structure and grafting rate, 101851321 B of Chinese patent CN use
The technique of suspension polymerisation is prepared for terpolymer styrene-acrylonitrile-glycidyl methacrylate（SAG）, by this
Method can control the content of epoxy group, and the grafting rate of epoxy group is up to 10%.Therefore, it can be obtained by way of copolymerization
Obtain the graft copolymer of high grafting rate.On this basis, 103421154 A of Chinese patent CN disclose a kind of containing reactive base
The comb-grafted copolymer and its preparation method and application of group.Compared with the line style graft copolymer of commercialization, the comb polymers
Object can effectively improve modulus, elongation at break, yield strength and tensile strength of PET/ABS alloys etc.（WY Dong, HT
Wang, MF He, et al. Industrial & Engineering Chemistry Research, 2015, 54:
2081-2089）.Nevertheless, the polymer segment of side chain is mainly methyl acrylic ester or esters of acrylic acid in the patent
The homopolymer of monomer, polarity is higher, is not suitable for low polar polyphenylene oxide or styrene-based polymer, therefore, prepares and contains epoxy
The graft copolymer of group and polystyrene and its derivative segment is of great significance and is worth.
Invention content
The primary purpose of the present invention is that for the disadvantage of existing polymer blend alloy strength difference, a kind of novel height is provided
The graft copolymer containing epoxy group of effect.
Another object of the present invention is to provide the preparation methods of the above-mentioned graft copolymer containing epoxy group.
The object of the invention is achieved through the following technical solutions：
A kind of graft copolymer containing epoxy group, the graft copolymer are side chain containing epoxy group and polystyrene and its spread out
A kind of polymer of biological segment is made by following substance reaction by weight percentage：
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 30wt% containing epoxy group；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing epoxy group is 10200 ~ 101000, preferably 11000 ~ 47000, and weight is equal
Molecular weight is 32000 ~ 200000, preferably 40000 ~ 95000.
The present invention using carbon-carbon double bonds high molecular polymer C and carbon-carbon double bonds monomer A, containing epoxy group not
Graft copolymer of the side chain containing epoxy group and polystyrene and its derivative segment is obtained by the reaction in saturation monomer B.High-content
Epoxy group can improve the binding force with polyester, and will gather after the high molecular polymer C copolymerization of carbon-carbon double bonds in the present invention
Styrene and its derivatives segment introduces side chain, has better binding force with polyphenylene oxide or styrene-based polymer.The present invention
The graft copolymerization for high the grafting rate line style and comb-type structure that the graft copolymer containing epoxy group prepared is obtained with the prior art
Object is compared, can more be effectively improved in the case of close molecular weight and epoxy group content polyphenylene oxide or styrene-based polymer with
The intensity of polyester alloy.
It is further preferred that the graft copolymer containing epoxy group, by weight percentage, by following substance reaction
It is made：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing epoxy group；
The high molecular polymer C of 10wt% ~ 20wt% carbon-carbon double bonds.
The high molecular polymer C of the carbon-carbon double bonds is reacted with the monomer E of carbon-carbon double bonds by high molecular polymer D
It obtains, wherein the high molecular polymer D chemical general formulas are：
Wherein R1For hydrogen atom, methyl or ethyl, the integer that m is 20 ~ 120, the integer that n is 2 ~ 12；S is sulphur atom, and G is epoxy
Group is carboxyl, amino or hydroxyl；
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 selected from acrylamide, Methacrylamide, Glycidyl methacrylate
Glyceride, allyl glycidyl ether, acryloyl chloride, methacrylic chloride, methylacryoyloxyethyl isocyanates and its spread out
One or more of biology.
Preferably, the high molecular polymer C number-average molecular weights of the carbon-carbon double bonds are 3000 ~ 13000.
Preferably, the monomer A of the carbon-carbon double bonds be selected from styrene, α-methylstyrene, α-ethyl styrene and its
It is one or more of in derivative.
Preferably, the unsaturated monomer B containing epoxy group is selected from glycidyl methacrylate, allyl glycidyl
One or more of glycerin ether and its derivative.
The viscous state temperature of graft copolymer of the present invention containing epoxy group be 150 DEG C ~ 200 DEG C, preferably 160
℃~190℃.It is unfavorable for the melt blending of graft copolymer when viscous state temperature being less than 150 DEG C or higher than 200 DEG C.
The present invention also provides the preparation methods of the above-mentioned graft copolymer containing epoxy group, include the following steps：
The high molecular polymer C of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing epoxy group are led to
Free radical polymerisation process is crossed to be copolymerized.
The free radical polymerisation process is bulk polymerization, polymerisation in solution, suspension polymerisation or emulsion polymerization, is that this field is normal
The preparation method of rule, the specific method is as follows：
The bulk polymerization preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing epoxy group with it is carbon containing
The high molecular polymer C and initiator of carbon double bond slowly heat up after mixing, after reacting 1 ~ 10h at 40 DEG C ~ 100 DEG C, do
The graft copolymer containing epoxy group is obtained after dry.
The polymerisation in solution preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing epoxy group, contain
High molecular polymer C, organic solvent and the initiator of carbon-carbon double bond slowly heat up after mixing, are reacted at 40 DEG C ~ 100 DEG C
After 1 ~ 10h, the graft copolymer containing epoxy group is obtained after devolatilization drying.
The suspension polymerization preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing epoxy group, contain
High molecular polymer C, water, dispersant and the initiator of carbon-carbon double bond slowly heat up after mixing, anti-at 40 DEG C ~ 100 DEG C
The graft copolymer containing epoxy group is obtained after answering 1 ~ 10h, after filtration drying.
The emulsion-polymerizing preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing epoxy group, contain
High molecular polymer C, water, emulsifier and the initiator of carbon-carbon double bond slowly heat up after mixing, anti-at 40 DEG C ~ 100 DEG C
After answering 1 ~ 10h, the graft copolymer containing epoxy group is obtained after dry.
Wherein, the preparation method of the high molecular polymer C of the carbon-carbon double bonds, includes the following steps：
Under the conditions of existing for chain-transferring agent, by one in styrene, α-methylstyrene, α-ethyl styrene and its derivative
Kind or several initiators that pass through cause the obtained high molecular polymer D of free radical polymerization；Then by obtained high molecular polymer D with
The monomer E of carbon-carbon double bonds reacts at room temperature, obtains the high molecular polymer C of carbon-carbon double bonds.
The molar ratio of the high molecular polymer D and the monomer E of carbon-carbon double bonds are 1:0.8~1.3.
The chain-transferring agent is one or more of the aliphatic mercaptan containing carboxyl, hydroxyl or amino, specific such as mercapto
Base propyl alcohol, mercaptoethanol, sulfydryls hexanol, mercaptoundecanol, thioacetic acid, mercaptopropionic acid, dimercaptosuccinic acid, mercaptohexanoic acid, mercapto
Base hendecanoic acid, sulfydryl lauric acid/dodecanoic acid, mercaptoethylmaine, 3- sulfydryl -1- propylamine etc..
The initiator is one kind or several in azo-initiator, peroxide initiator or redox initiator
Kind, it is specific such as azodiisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azo-bis-iso-dimethyl, two hexamethylene of azo
Base formonitrile HCN, azo-bis-isobutyrate hydrochloride, azo dicyano valeric acid, lauroyl peroxide, benzoyl peroxide, hydrogen peroxide are different
Propyl benzene, tert-butyl hydroperoxide, di-cyclohexylperoxy di-carbonate, potassium peroxydisulfate, ammonium persulfate, (NH4)2S2O8-FeSO4、It crosses
Aoxidize dibenzoyl-N, N dimethyl aniline, ammonium persulfate-sodium bisulfite etc..
Catalyst and inhibition can be according to circumstances added when being reacted with the monomer E of carbon-carbon double bonds in high molecular polymer D in right amount
Agent, the catalyst are tertiary amine catalyst, specific such as N, N- dimethyl benzylamines, triethylamine, N, N- dimethyl cyclohexyl amines, double
(2- dimethylaminoethyls) ether, n-ethylpiperazine etc..
The polymerization inhibitor is radical polymerization inhibitor, specific such as hydroquinone, p-tert-Butylcatechol, methylnaphthohydroquinone, sulphur
Diphenylamines, nitrosobenzene, m-dinitrobenzene, 1,4-benzoquinone, p-hydroxyanisole, stannous chloride, ferric trichloride, phosphorous triphenyl phosphate
Ester etc..
Graft copolymer of the present invention containing epoxy group can be the particle made by pelleter, comminutor, also may be used
To be the powder of pulverizer making.
The present invention also provides the above-mentioned graft copolymers containing epoxy group to improve polyphenylene oxide or styrene-based polymer
With the application in the intensity of polyester alloy.
Compared with prior art, the present invention has the advantages that：
Graft copolymer containing epoxy group prepared by the present invention can improve polyphenylene oxide or styrene-based polymer and be closed with polyester
The epoxy group of the intensity of gold, high-content can improve the polystyrene introduced with polyester binding force, side chain and its derivative chain
Section can improve the binding force with another phase polyphenylene oxide or styrene-based polymer.The high grafting rate line style obtained with the prior art
It compares, can preferably be improved in the case of similar molecular weight and epoxy group content poly- with the graft copolymer of comb-type structure
The intensity of phenylate or styrene-based polymer and polyester alloy.
Specific implementation mode
Explanation is further expalined to the present invention with reference to specific embodiment, 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 be included within the protection domain of the claims in the present invention.
In following embodiment, raw material used is commercial goods.
Test and characterizing method
（One）Examination of infrared spectrum
Tabletting after the graft copolymer containing epoxy group of acquisition is milled with the potassium bromide after drying, is placed on Fourier transform
Infrared spectrometer is tested.4000 ~ 400cm of scanning range-1, resolution ratio 4cm-1, scanning times 16 times.
（Two）Gel permeation chromatography（GPC）Test
After the graft copolymer containing epoxy group of acquisition is dissolved with tetrahydrofuran, is measured and polymerize using gel permeation chromatograph
The retention time of object, detecting instrument are refraction index analyzer, and mobile phase is tetrahydrofuran, using monodisperse polystyrene conduct
Standard specimen calculates the weight average molecular weight and number-average molecular weight of polymer.
（Three）Viscous state temperature test
By the graft copolymer containing epoxy group of acquisition after heating melts, the thin slice that thickness is about 2mm is made, and use
Thermomechanical analyzer（TMA）The temperature strain curve for testing copolymer, the viscosity flow of copolymer is obtained according to temperature strain curve
State temperature.
Embodiment 1
It is under nitrogen protection, 80g styrene, 20g α-methylstyrenes, 1.5g chain-transferring agents mercaprol, 4.5g initiators is even
After nitrogen bis-isobutyronitrile and 200g solvent toluenes are mixed evenly, the four-hole bottle equipped with agitating paddle, condenser and thermometer is moved to
In, 65 DEG C are heated to, after reacting 6h, obtains the toluene solution of pbz polymer polymer D；Reaction system is down to room temperature, is added
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（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:1.2）, after reaction 8h is stirred at room temperature, product is revolved
Be evaporated it is dry after, obtain the high molecular polymer C of carbon-carbon double bonds, pass through the number of high molecular polymer C obtained known to GPC tests
Average molecular weight is about 4800.
Under nitrogen protection, by 120g styrene, 20g glycidyl methacrylate, the carbon-carbon double of the above-mentioned preparations of 10g
After high molecular polymer C, 4.5g azodiisobutyronitrile and 150g toluene of key are mixed evenly（The monomer A of carbon-carbon double bonds,
The high molecular polymer C dosages of unsaturated monomer B and carbon-carbon double bonds containing epoxy group are 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, by product
After revolving is dry, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；By GPC
Test, graft copolymer number-average molecular weight of the gained containing epoxy group is about 20200, weight average molecular weight 51600；Gained contains ring
The graft copolymer viscous state temperature of oxygen groups is about 168 DEG C.
Embodiment 2
It is under nitrogen protection, 60g styrene, 50g α-ethyl styrene, 1.5g chain-transferring agents mercaprol, 3.5g initiators is even
After nitrogen bis-isobutyronitrile and 250g solvent xylenes are mixed evenly, four mouthfuls equipped with agitating paddle, condenser and thermometer are moved to
In bottle, 65 DEG C are heated to, after reacting 6h, obtains the xylene solution of pbz polymer polymer D；Reaction system is down to room temperature,
The monomer E metering systems of addition 0.01g polymerization inhibitors phenothiazine, 0.02g catalyst of triethylamine and 1.36g carbon-carbon double bonds
Acyl chlorides（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:0.8）, after reaction 5h is stirred at room temperature, product is revolved
Be evaporated it is dry after, obtain the high molecular polymer C of carbon-carbon double bonds.Number by the high molecular polymer C obtained known to GPC tests
Average molecular weight is about 5310.
Under nitrogen protection, by 110g styrene, 20g α-methylstyrenes, 16g glycidyl methacrylate, 54g
High molecular polymer C, 2.1g azodiisobutyronitrile and 300g butyl acetates of the carbon-carbon double bonds of above-mentioned preparation are mixed equal
After even（The high molecular polymer C dosages of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing epoxy group
Respectively 65.00wt%, 8.00wt% and 27.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, add
Heat is to 75 DEG C, after reacting 6h, after product revolving drying, obtains graft copolymer.By infrared spectrum it is found that obtained grafting is total to
Polymers contains epoxy group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing epoxy group is about 31200, weight
Average molecular weight is 70700；Graft copolymer viscous state temperature of the gained containing epoxy group is about 189 DEG C.
Embodiment 3
Under nitrogen protection, by 80g styrene, 40g α-methylstyrenes, 2g chain-transferring agents mercaptoethanol, 1.2g initiator azos
After two different heptonitriles and 150g solvent ethyl acetates are mixed evenly, four mouthfuls equipped with agitating paddle, condenser and thermometer are moved to
In bottle, 70 DEG C are heated to, after reacting 5h, obtains the ethyl acetate solution of pbz polymer polymer D；Reaction system is down to room
0.01g polymerization inhibitors nitrosobenzene, 0.02g catalyst ns, the monomer E of N- dimethyl cyclohexyl amines and 5.0g carbon-carbon double bonds is added in temperature
Isocyanatoethyl（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:1.25）, it is stirred at room temperature
After reacting 10h, after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.By being obtained known to GPC tests
The number-average molecular weight of high molecular polymer C be about 12880.
Under nitrogen protection, by 120g α-methylstyrenes, 15g glycidyl methacrylate, 15g above-mentioned preparations
After high molecular polymer C, 1.6g benzoyl peroxide and 150g toluene of carbon-carbon double bonds are mixed evenly（Carbon-carbon double bonds
Monomer A, unsaturated monomer B and carbon-carbon double bonds containing epoxy group high molecular polymer C dosages be respectively 80.00wt%,
10.00wt% and 10.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 80 DEG C, react 8h
Afterwards, by after product revolving drying, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymer contains epoxy group
Group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing epoxy group is about 47500, and weight average molecular weight is
99100；Graft copolymer viscous state temperature of the gained containing epoxy group is about 197 DEG C.
Embodiment 4
Under nitrogen protection, by 50g styrene, 50g α-ethyl styrene, 2g chain-transferring agents thioacetic acid, 1.6g initiator azos
After two different heptonitriles and 150g solvent xylenes 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 xylene solution of pbz polymer polymer D；It is down to room temperature, 0.01g inhibitions are added
The monomer E glycidyl methacrylate of agent 1,4-benzoquinone, 0.02g catalyst ns-ethyl piperazidine and 4.0g carbon-carbon double bonds（It is high
The monomer E molar ratios of Molecularly Imprinted Polymer D and carbon-carbon double bonds are 1:1.3）, be warming up to 130 DEG C be stirred to react 12h after, by product
After revolving is dry, the high molecular polymer C of carbon-carbon double bonds is obtained.Understand obtained high molecular polymer C's by GPC tests
Number-average molecular weight is about 9800.
Under nitrogen protection, by 90g styrene, 5g allyl glycidyl ethers, the above-mentioned preparations of 5g carbon-carbon double bonds height
After Molecularly Imprinted Polymer C, 1.6g azodiisobutyronitrile and 100g toluene are mixed evenly（The monomer A of carbon-carbon double bonds, contain epoxy
The unsaturated monomer B of group and the high molecular polymer C dosages of carbon-carbon double bonds be respectively 90.00wt%, 5.00wt% and
5.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 75 DEG C, after reacting 8h, product is revolved
Be evaporated it is dry after, obtain graft copolymer.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；It is surveyed by GPC
Examination, graft copolymer number-average molecular weight of the gained containing epoxy group is about 31900, weight average molecular weight 66700；Gained contains epoxy
The graft copolymer viscous state temperature of group is about 173 DEG C.
Embodiment 5
It is under nitrogen protection, 100g styrene, 2g chain-transferring agents thioacetic acid, 1.8g initiators azobisisoheptonitrile and 120g is molten
It after agent dimethylbenzene is mixed evenly, moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, is heated to 70 DEG C, instead
After answering 5h, the xylene solution of pbz polymer polymer D is obtained；It is down to room temperature, 0.01g polymerization inhibitors stannous chloride, 0.02g is added
The monomer E glycidyl methacrylate of catalyst bis- (2- dimethylaminoethyls) ethers and 2.4g carbon-carbon double bonds（Macromolecule
The monomer E molar ratios of polymer D and carbon-carbon double bonds are 1:0.8）, be warming up to 130 DEG C be stirred to react 12h after, product is rotated
After drying, the high molecular polymer C of carbon-carbon double bonds is obtained.The number of high molecular polymer C by being obtained known to GPC tests is equal
Molecular weight is about 12900.
Under nitrogen protection, by 100g styrene, 60g glycidyl methacrylate, the carbon-carbon double of the above-mentioned preparations of 40g
After high molecular polymer C, 1.5g benzoyl peroxide and 300g toluene of key are mixed evenly（The monomer A of carbon-carbon double bonds,
The high molecular polymer C dosages of unsaturated monomer B and carbon-carbon double bonds containing epoxy group are 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, will produce
After object revolving is dry, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；By
GPC is tested, and graft copolymer number-average molecular weight of the gained containing epoxy group is about 54100, weight average molecular weight 103300；Gained
Graft copolymer viscous state temperature containing epoxy group is about 182 DEG C.
Embodiment 6
It is under nitrogen protection, 40g styrene, 60g α-methylstyrenes, 2.4g chain-transferring agents mercaptoethylmaine, 5.0g initiators is even
After nitrogen diisoamyl nitrile and 250g ethyl acetate are mixed evenly, the four-hole bottle equipped with agitating paddle, condenser and thermometer is moved to
In, 65 DEG C are heated to, after reacting 7h, obtains the ethyl acetate solution of pbz polymer polymer D；It is down to room temperature, 0.02g resistances are added
The monomer E isocyanatoethyls of poly- agent hydroquinone and 4.8g carbon-carbon double bonds（High molecular polymer D and carbon containing carbon
The monomer E molar ratios of double bond are 1:1）, after reaction 8h is stirred at room temperature, after product revolving drying, obtain the height of carbon-carbon double bonds
Molecularly Imprinted Polymer C.Number-average molecular weight by the high molecular polymer C obtained known to GPC tests is about 3100.
Under nitrogen protection, by 80g styrene, 10g glycidyl methacrylate, the carbon-carbon double of the above-mentioned preparations of 10g
After high molecular polymer C, 4.5g azodiisobutyronitrile and 250g toluene of key are mixed evenly（The monomer A of carbon-carbon double bonds,
The high molecular polymer C dosages of unsaturated monomer B and carbon-carbon double bonds containing epoxy group are respectively 80.00wt%, 10.00wt%
And 10.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 75 DEG C, after reacting 6h, will produce
After object revolving is dry, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；By
GPC is tested, and graft copolymer number-average molecular weight of the gained containing epoxy group is about 10400, weight average molecular weight 34900；Gained
Graft copolymer viscous state temperature containing epoxy group is about 154 DEG C.
Embodiment 7
Under nitrogen protection, by 10g styrene, 90g α-ethyl styrene, 2.4g chain-transferring agent sulfydryls lauric acid/dodecanoic acid, 2.1g initiators
After azodiisobutyronitrile and 150g toluene are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer,
70 DEG C are heated to, after reacting 5h, obtains the toluene solution of pbz polymer polymer D；Be added 0.02g hydroquinone of polymerization retarder and
The monomer E dimethylamino-propyl Methacrylamides of 1.6g carbon-carbon double bonds（The monomer of high molecular polymer D and carbon-carbon double bonds
E molar ratios are 1:1）, after being stirred to react 8h, after product revolving drying, obtain the high molecular polymer C of carbon-carbon double bonds.It is logical
The number-average molecular weight for crossing the high molecular polymer C obtained known to GPC tests is about 8500.
By 98g styrene, the polyphosphazene polymer of 10g glycidyl methacrylate, the carbon-carbon double bonds of the above-mentioned preparations of 12g
Close object C, 2.4 g anion emulsifiers lauryl sodium sulfate, 1.2g nonionic emulsifier polyoxethylene octylphenyls phenol ether, 0.9g
Homogenizer high-speed stirred 15min is used after initiator potassium persulfate and the mixing of 175g distilled water, obtains pre-emulsion（It is carbon containing
The monomer A of carbon double bond, unsaturated monomer B and carbon-carbon double bonds containing epoxy group high molecular polymer C dosages be respectively
81.67wt%, 8.33wt% and 10.00wt%）；The pre-emulsion of acquisition is moved to four equipped with agitating paddle, condenser and thermometer
In mouth bottle, nitrogen atmosphere protection is heated to 75 DEG C, after reacting 8h, is cooled to room temperature, the CaCl of 10 ml a concentration of 5% is added2Water
Solution, demulsification are washed product repeatedly with distilled water after precipitating, and are crushed after then drying, are obtained graft copolymer.By infrared light
Spectrum is it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, graft copolymer number of the gained containing epoxy group
Average molecular weight is about 79100, weight average molecular weight 179500；Graft copolymer viscous state temperature of the gained containing epoxy group be about
193℃。
Embodiment 8
It is under nitrogen protection, 40g styrene, 60g α-ethyl styrene, 2.4g chain-transferring agents mercaptoethylmaine, 4.2g initiators is even
After nitrogen diisoamyl nitrile and 250g toluene 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 toluene solution of pbz polymer polymer D to 65 DEG C；0.02g polymerization inhibitors are added to benzene
The monomer E isocyanatoethyls of diphenol and 4.8g carbon-carbon double bonds（The list of high molecular polymer D and carbon-carbon double bonds
Body E molar ratios are 1:1）, after reaction 8h is stirred at room temperature, after product revolving drying, obtain the high molecular polymerization of carbon-carbon double bonds
Object C.Number-average molecular weight by the high molecular polymer C obtained known to GPC tests is about 4500.
2g calcium phosphate and 2g sodium sulphate are dissolved in 150g distilled water, moved to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in；By 80g styrene, 10g allyl glycidyl ethers, 1.5g initiators (NH4)2S2O8-FeSO4, the above-mentioned systems of 30g
The high molecular polymer C of standby carbon-carbon double bonds is after mixing（The monomer A of carbon-carbon double bonds, the unsaturation containing epoxy group
The high molecular polymer C dosages of monomer B and carbon-carbon double bonds are respectively 66.67wt%, 8.33wt% and 25.00wt%）, in addition
It states in four-hole bottle, nitrogen atmosphere protection is heated to 65 DEG C, after reacting 7h, product is washed and is filtered, graft copolymerization is obtained after dry
Object.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；It is tested by GPC, gained connecing containing epoxy group
Graft copolymer number-average molecular weight is about 97400, weight average molecular weight 194100；Graft copolymer viscosity flow of the gained containing epoxy group
State temperature is about 198 DEG C.
Embodiment 9
It is under nitrogen protection, 80g styrene, 20g α-methylstyrenes, 1.5g chain-transferring agents mercaprol, 1.6g initiators is even
After nitrogen bis-isobutyronitrile and 130g solvent toluenes are mixed evenly, the four-hole bottle equipped with agitating paddle, condenser and thermometer is moved to
In, 65 DEG C are heated to, after reacting 6h, obtains the toluene solution of pbz polymer polymer D；Reaction system is down to room temperature, is added
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（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:1.2）, after reaction 8h is stirred at room temperature, product is revolved
Be evaporated it is dry after, obtain the high molecular polymer C of carbon-carbon double bonds, pass through the number of high molecular polymer C obtained known to GPC tests
Average molecular weight is about 10890.
Under nitrogen protection, by 120g styrene, 20g glycidyl methacrylate, the carbon-carbon double of the above-mentioned preparations of 10g
After high molecular polymer C, 1.8g azodiisobutyronitrile and 120g toluene of key are mixed evenly（The monomer A of carbon-carbon double bonds,
The high molecular polymer C dosages of unsaturated monomer B and carbon-carbon double bonds containing epoxy group are 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, by product
After revolving is dry, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymer contains epoxy group；By GPC
Test, graft copolymer number-average molecular weight of the gained containing epoxy group is about 61500, weight average molecular weight 118300；Gained contains
The graft copolymer viscous state temperature of epoxy group is about 198 DEG C.
Comparative example 1
Under nitrogen protection, 100g styrene, 30g α-methylstyrenes, 20g glycidyl methacrylate, 2.1g are caused
After agent azodiisobutyronitrile and 180g solvent toluenes are mixed evenly, four equipped with agitating paddle, condenser and thermometer are moved to
In mouth bottle, 75 DEG C are heated to, after reacting 6h, is down to room temperature, after product revolving drying, obtains linear copolymers.By infrared light
Spectrum is it is found that obtained linear copolymers contain epoxy group；It is tested by GPC, linear copolymers number of the gained containing epoxy group
Average molecular weight is about 20120, weight average molecular weight 50500.
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, moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated 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 methacrylic acids is added
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,
Number-average molecular weight by the high molecular polymer C obtained known to GPC tests is about 4100.
Under nitrogen protection, by 120g methyl methacrylates, 20g glycidyl methacrylate, 10g above-mentioned preparations
After high molecular polymer C, 1.4g azodiisobutyronitrile and 240g toluene of carbon-carbon double bonds are mixed evenly, move to be equipped with and stir
In the four-hole bottle for mixing paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, combed is obtained and connects
Graft copolymer.By infrared spectrum it is found that obtained comb-grafted copolymer contains epoxy group；It is tested by GPC, gained contains ring
The comb-grafted copolymer number-average molecular weight of oxygen groups is about 19970, weight average molecular weight 50660.
Application performance test
The graft copolymer containing epoxy group obtained in comparative example 1, comparative example 2 and embodiment 1-9 is applied to prepare polyphenyl
Ether（PPE）With polybutylene terephthalate (PBT)（PBT）Alloy, and compared with Commercial epoxy analog copolymer SAG.Wherein PPE/
50 parts of PPE in PBT alloy formula, 48 parts of PBT, 2 parts of graft copolymer；Blank sample is 50 parts of PPE, 50 parts of PBT.
Raw material PPE and PBT dry 4h in 120 DEG C of baking ovens respectively, spare.Each material is uniformly mixed addition twin-screw to squeeze
Go out machine spout extruding pelletization, squeezes out that material strip is water cooled by sink, is sent into pelleter pelletizing after drying obtains PPE/PBT conjunctions
Injection molding machine hopper is added in 120 DEG C of the Alloy plastic particle drying 4 hours of acquisition by gold, sets corresponding Shooting Technique, injection molding pressure
Film is molded to obtain the standard batten of test.Tensile property：By ISO 527/2-93 standard testings, tensile speed is 50 mm/
min；Bending strength：By ISO 178-93 standard testings, rate of bending is 2 mm/min；Test result is as shown in table 1.
1 PPE/PBT alloy properties of table
As shown in Table 1, PPE/PBT alloy materials tensile strength and the bending strength for not adding graft copolymer are relatively low.Addition connects
The tensile strength and bending strength of graft copolymer alloy product increase.As can be seen that the epoxy group that contains prepared by the present invention is grafted
Copolymer effect is better than common epoxy quasi-graft copolymer on the market at present；Embodiment 1 is compared with comparative example 1,2, close
Molecular weight and epoxy group content under the conditions of, the graft copolymer containing epoxy group prepared by the present invention is obtained than the prior art
Line style and the graft copolymer of comb-type structure can preferably improve the intensity of alloy.
Claims (13)
1. a kind of graft copolymer containing epoxy group, which is characterized in that the graft copolymer be side chain containing epoxy group and
A kind of polymer of polystyrene and its derivative segment is made by following substance reaction by weight percentage：
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 30wt% containing epoxy group；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing epoxy group is 10200 ~ 101000, preferably 11000 ~ 47000, and weight is equal
Molecular weight is 32000 ~ 200000, preferably 40000 ~ 95000.
2. the graft copolymer containing epoxy group according to claim 1, which is characterized in that by weight percentage, by with
Lower substance reaction is made：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing epoxy group；
The high molecular polymer C of 10wt% ~ 20wt% carbon-carbon double bonds.
3. the graft copolymer according to claim 1 or claim 2 containing epoxy group, 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 high molecular polymer D and carbon-carbon double bonds, wherein the high molecular polymer D
Chemical general formula is：
Wherein R1For hydrogen atom, methyl or ethyl, the integer that m is 20 ~ 120, the integer that n is 2 ~ 12；S is sulphur atom, and G is epoxy
Group is carboxyl, amino or hydroxyl；
The monomer E of the carbon-carbon double bonds carries epoxy group, amino, isocyanate group or acid chloride group.
4. the graft copolymer containing epoxy group according to claim 3, which is characterized in that the monomer of the carbon-carbon double bonds
E is selected from acrylamide, Methacrylamide, glycidyl methacrylate, allyl glycidyl ether, acryloyl chloride, first
One or more of base acryloyl chloride, methylacryoyloxyethyl isocyanates and its derivative.
5. the graft copolymer containing epoxy group according to claim 3, which is characterized in that the high score of the carbon-carbon double bonds
The number-average molecular weight of sub- polymer C is 3000 ~ 13000.
6. the graft copolymer according to claim 1 or claim 2 containing epoxy group, which is characterized in that the carbon-carbon double bonds
Monomer A is one or more of in styrene, α-methylstyrene, α-ethyl styrene and its derivative.
7. the graft copolymer according to claim 1 or claim 2 containing epoxy group, which is characterized in that described containing epoxy group
Unsaturated monomer B is selected from one or more of glycidyl methacrylate, allyl glycidyl ether and its derivative.
8. the graft copolymer according to claim 1 or claim 2 containing epoxy group, which is characterized in that described containing epoxy group
The viscous state temperature of graft copolymer is 150 DEG C ~ 200 DEG C, preferably 160 DEG C ~ 190 DEG C.
9. the preparation method of the graft copolymer containing epoxy group described in claim any one of 1-8, which is characterized in that including such as
Lower step：
The high molecular polymer C of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing epoxy group are led to
Free radical polymerisation process is crossed to be copolymerized；The free radical polymerisation process is bulk polymerization, polymerisation in solution, suspension polymerisation or lotion
Polymerization.
10. the preparation method of the graft copolymer containing epoxy group according to claim 9, which is characterized in that described carbon containing
The preparation method of the high molecular polymer C of carbon double bond, includes the following steps：
Under the conditions of existing for chain-transferring agent, by one in styrene, α-methylstyrene, α-ethyl styrene and its derivative
Kind or several initiators that pass through cause the obtained high molecular polymer D of free radical polymerization；Then by obtained high molecular polymer D with
The monomer E of carbon-carbon double bonds reacts at room temperature, obtains the high molecular polymer C of carbon-carbon double bonds.
11. the preparation method of the graft copolymer containing epoxy group according to claim 10, which is characterized in that the high score
The molar ratio of sub- polymer D and the monomer E of carbon-carbon double bonds are 1:0.8~1.3.
12. the preparation method of the graft copolymer containing epoxy group according to claim 10, which is characterized in that the chain turns
Shifting agent is one or more of the aliphatic mercaptan containing carboxyl, hydroxyl or amino；The initiator be azo-initiator,
One or more of peroxide initiator or redox initiator.
13. the graft copolymer containing epoxy group described in claim any one of 1-8 is improving polyphenylene oxide or styryl polymerization
Application in the intensity of object and polyester alloy.
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| CN112979966A (en) * | 2019-12-17 | 2021-06-18 | 万华化学集团股份有限公司 | Comb-structured polymer and preparation method and application thereof |
| CN113968975A (en) * | 2020-07-21 | 2022-01-25 | 万华化学集团股份有限公司 | Block structure polymer, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256442A (en) * | 1993-03-04 | 1994-09-13 | Mitsubishi Petrochem Co Ltd | Production of graft copolymer |
| 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 |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256442A (en) * | 1993-03-04 | 1994-09-13 | Mitsubishi Petrochem Co Ltd | Production of graft copolymer |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979966A (en) * | 2019-12-17 | 2021-06-18 | 万华化学集团股份有限公司 | Comb-structured polymer and preparation method and application thereof |
| CN113968975A (en) * | 2020-07-21 | 2022-01-25 | 万华化学集团股份有限公司 | Block structure polymer, preparation method and application thereof |
| CN113968975B (en) * | 2020-07-21 | 2022-11-04 | 万华化学集团股份有限公司 | Block structure polymer, preparation method and application thereof |
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