CN104610515B - A kind of comb-shaped graft copolymer containing reactive group and preparation method and application - Google Patents
A kind of comb-shaped graft copolymer containing reactive group and preparation method and application Download PDFInfo
- Publication number
- CN104610515B CN104610515B CN201410816060.0A CN201410816060A CN104610515B CN 104610515 B CN104610515 B CN 104610515B CN 201410816060 A CN201410816060 A CN 201410816060A CN 104610515 B CN104610515 B CN 104610515B
- Authority
- CN
- China
- Prior art keywords
- macromonomer
- monomer
- comb
- graft copolymer
- shaped graft
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention discloses a kind of comb-shaped graft copolymer containing reactive group and preparation method and application.Small molecule monomer A and macromonomer B are copolymerized to form the comb-shaped graft copolymer that main chain is small molecule monomer A, side chain is macromonomer B；The weight of macromonomer B is that the weight of the 0.1wt ﹪~80wt ﹪, small molecule monomer A of comb-shaped graft copolymer quality are 99.9wt ﹪~20wt ﹪ of comb-shaped graft copolymer quality.Present copolymer contains the comb-shaped graft copolymer of reactive group for side chain, can be used as bulking agent, chain extender.
Description
Technical field
The invention belongs to polymeric material field, is related to a kind of containing the comb-shaped graft copolymer of reactive group and its preparation side
Method and application, and in particular to poly- (methyl) methyl acrylate of a kind of comb shape containing reactive group and its preparation method and application.
Background technology
Comb-shaped graft copolymer is to be formed by connecting by two kinds of different macromolecular chains with chemical bond.One of them is by A
The macromolecule trunk (skeleton) of unit composition, i.e. main chain；The other is the macromolecule branch being made of unit B, i.e. side chain.Pass through
The approach that side chain is attached to main chain is had three kinds by covalent bond, is Graft to, Graft through and Graft from respectively.
So-called Graft through methods, are the side chains of first synthetic macromolecule, using polymerization end with double bond or other anti-
The macromonomer of group is answered to be aggregating so as to prepare comb shape graft polymers.The advantages of Graft through methods is energy
The grafting density and structural integrity of enough comb shape graft polymers of control well.
The demand for development high molecular material of modern science and technology has many, very high comprehensive performance.Such as, it is desirable to
Some plastics not only high temperature resistant, but also be easy to processing and forming；Not only high intensity is required, but also requires good toughness；Both there is excellent mechanical property
Can, and with some specific functions etc..Obviously, single high polymer is difficult to meet these high performance requirements.Meanwhile will
Develop a kind of brand-new material to be also not easy, not only time length, cost is big, and difficulty is also at a relatively high；In contrast, using
Some high molecular materials carry out blending and modifying and prepare high performance material, not only simple and direct effective, but also pretty economical.The sixties with
Come, polymer blending modification technology develops rapidly, it makes the characteristic of different polymer excellent by the blending of multiple polymers
Change is combined in one, is significantly improved material property, or assigns the brand-new performance that original copolymer does not have, and is macromolecule
Material opens a wide approach.
High polymer alloy is the compound system being made of two or more high molecular material, is by two specifically
Kind or two or more different types of resins, either resin and a small amount of rubber or resin and a small amount of thermoplastic elastomer (TPE), are melting
Melt under state, the compound system prepared by blending.But high polymer alloy belongs to Immiscible Polymer Blends more, there is practicality to obtain
The high molecule alloy material of value, it is necessary to which form control and interface modification are carried out to incompatible Polymer Systems.Reactive compatibilization
Agent occurs chemical reaction by autoreactivity group and other high molecular components and forms chemical bond so as to fulfill increase-volume, therefore,
It prepares key is how to introduce high activity reactive functional groups in the polymer, and relatively simple method is to use appropriate change
Reaction is learned, makes main polymer chain, reactive group on side chain or end group band.
The applicant discloses a kind of comb shape graft polymers containing reactive group in 103421154 A of patent CN
And preparation method and application.In that patent, reactive group is located on molecular backbone, during reactively blending, instead
Chemical reaction between answering property group and complementation group will be disturbed be subject to graft side chain space steric effect.
The content of the invention
It is an object of the invention in view of the deficiencies of the prior art, there is provided a kind of comb shape graft copolymerization containing reactive group
Thing, is poly- (methyl) methyl acrylate of the comb shape that side chain contains reactive group specifically.
Present copolymer is the comb-shaped graft copolymer that main chain is small molecule monomer A, side chain is macromonomer B；Greatly
The weight of molecule monomer B is comb shape for the weight of the 0.1wt ﹪~80wt ﹪, small molecule monomer A of comb-shaped graft copolymer quality
99.9wt ﹪~20wt ﹪ of graft copolymerization amount of substance；
The number-average molecular weight of the comb-shaped graft copolymer is 5000~100000；
Preferably, the weight of small molecule monomer A is 80wt ﹪~50wt ﹪ of comb-shaped graft copolymer quality；
Preferably, the weight of macromonomer B is 5wt ﹪~50wt ﹪ of comb-shaped graft copolymer quality；
Preferably, the number-average molecular weight of comb-shaped graft copolymer is 15000~60000；
The macromonomer B is represented with general formula (1)：
Wherein R1、R2For hydrogen atom or methyl, R3For methyl, ethyl, butyl, the tert-butyl group or glycidyl, R4For
Hydrogen atom or sec-butyl, X expressions-CH2CH(OH)CH2- or-Z-NHCO-, Y be-L1-L2- S-, Z are-(CH2CH2O)a
(CH2)b-,L1For Direct Bonding ,-O- ,-COO- or-NH-, L2For C1~C20 alkylidenes or C6~C20 aryl, S is represented
Sulphur atom, n are 5~100 integer, and the integer that m is 0 or 1, a are 0~20, b is 1~20 integer；
The small molecule monomer A is methacrylate, acrylate, hydroxyl ester, Methacrylamide, unsaturation
The one or more of nitrile, styrene monomer and its derivative.
The number-average molecular weight of the macromonomer B is 500~10000.
It is a further object to provide a kind of preparation method of the comb-shaped graft copolymer containing reactive group, the party
Method be small molecule monomer A and macromonomer B are copolymerized to be formed main chain be small molecule monomer A, side chain be macromonomer B
Comb-shaped graft copolymer；The addition of macromonomer B for comb-shaped graft copolymer quality 0.1wt ﹪~80wt ﹪, small point
The addition of sub- monomer A is 99.9wt ﹪~20wt ﹪ of comb-shaped graft copolymer quality.
The number-average molecular weight of the comb-shaped graft copolymer is 5000~100000.
The copolymerization process can be polymerisation in bulk, polymerisation in solution, emulsion polymerization or suspension polymerisation, for existing ripe skill
Art.
In mass polymerization, using following methods：Under nitrogen protection, by polymerization initiator -1, chain-transferring agent, small point
Sub- monomer A, macromonomer B are mixed, and when reaction 1~10 is small at 50~120 DEG C, obtain comb-shaped graft copolymer.
The polymerization initiator -1 is all oil-soluble initiators.
The chain-transferring agent for lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid,
Isooctyl thioglycolate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate.
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Oil polymerization
Initiator -1 and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.001~5：100；Chain-transferring agent draws with polymerizeing
The molar ratio for sending out agent -1 is 0.1~10：1.
In solution polymerization process, using following methods：Under nitrogen protection, by polymerization initiator -2, chain-transferring agent, small point
Sub- monomer A, macromonomer B are dissolved in organic solvent, when reaction 1~10 is small at 50~120 DEG C.
The polymerization initiator -2 can be that water-soluble or oil-soluble initiator, the water soluble starter are institute
There is water soluble starter, the oil-soluble initiator is all oil-soluble initiators.
The chain-transferring agent for lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid,
Isooctyl thioglycolate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate.
The organic solvent is benzene,toluene,xylene, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, butyl acetate, the third two
Alcohol, dipropylene glycol methyl ether or dipropylene glycol.
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Polymerization is drawn
The mass ratio for sending out agent -2 and small molecule monomer A and macromonomer B total amounts is 0.001~5：100；Chain-transferring agent triggers with polymerizeing
The molar ratio of agent -2 is 0.1~10：1；Organic solvent and macromonomer B and the mass ratio of small molecule monomer B total amounts for 0.5~
5:1。
In suspension polymerization, using following methods：Under nitrogen protection, by polymerization initiator -3, chain-transferring agent, small point
Sub- monomer A, macromonomer B are mixed, be scattered under mechanical stirring dissolved with suspension stabilizer and suspension stabilization aid go from
In sub- water, when reaction 1~10 is small at 40~80 DEG C.
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Chain tra nsfer
The molar ratio of agent and polymerization initiator -3 is 0.1~10：1；Deionized water and small molecule monomer A and macromonomer B total amounts
Mass ratio is 0.5~10:1；Suspension stabilizer and the mass ratio of deionized water are 0.001~0.05:1；Suspension stabilizer with it is small
Molecule monomer A and the mass ratio of macromonomer B total amounts are 0.001~0.05:1；Suspension stabilizer and suspension stabilization aid
Mass ratio is 1~500:1；Polymerization initiator -3 and small molecule monomer A and the mass ratio of macromonomer B total amounts for 0.001~
5：100.
The polymerization initiator -3 is all oil-soluble initiators.
The chain-transferring agent for lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid,
Isooctyl thioglycolate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate.
The suspension stabilizer is organic suspending agent, the one or two of Inorganic suspending agent.
The suspension stabilization aid is disodium-hydrogen, sodium dihydrogen phosphate, sodium sulphate, sodium chloride, cetyl front three
One or more in base ammonium bromide, neopelex, dodecyl sodium sulfate, lauryl sodium sulfate.
In emulsion polymerization, using following methods：After emulsifying agent is dispersed in deionized water, small molecule is then added
The mixed liquor of monomer A, macromonomer B and chain-transferring agent, small molecule monomer A, macromonomer B are emulsified in deionized water,
It is passed through after nitrogen when adding that reaction 1~10 is small at polymerization initiator -4,40~80 DEG C, obtains comb-shaped graft copolymer.
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Emulsifying agent
Mass ratio with deionized water is 0.001~0.05:1；Polymerization initiator -4 and small molecule monomer A and macromonomer B total amounts
Mass ratio be 0.001~5：100；The molar ratio of chain-transferring agent and polymerization initiator -4 is 0.1~10：1；Emulsifying agent with small point
The mass ratio of sub- monomer A and macromonomer B total amounts is 0.001~0.1：1.
The polymerization initiator -4 is all water soluble starters.
The chain-transferring agent for lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid,
Isooctyl thioglycolate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate.
The emulsifying agent is cationic, anionic or non-ionic emulsifying agent.
The preparation method of the macromonomer B is：Using the mercaptan containing reactive hydrogen as chain-transferring agent, using free radical
Polymerisation polymerize (methyl) acrylate monomer, obtains the oligomer containing reactive hydrogen；Then obtained oligomer is being urged
Under the conditions of agent and polymerization inhibitor are existing, reacted with (methyl) acryloyl monomer containing energy and reactive with active hydrogen, 0~100 DEG C
It is lower reaction 1~10 it is small when, obtain macromonomer B.
The molar ratio of the mercaptan containing reactive hydrogen and (methyl) acrylate monomer is 0.01~0.5：1, it is excellent
Elect 0.01~0.3 as：1；The molar ratio of polymerization inhibitor and the oligomer containing reactive hydrogen is 0.001~0.1:1；Catalyst is with containing activity
The molar ratio of the oligomer of hydrogen is 0.001~0.1:1；Oligomer and energy and (methyl) propylene of reactive with active hydrogen containing reactive hydrogen
The molar ratio of acyl monomer is 0.3~1:1.
Described (methyl) acrylate monomer is methacrylate ester monomer or acrylate monomer；Methyl-prop
Olefin(e) acid ester system monomer is the monomer for including methacrylate unit in molecule, and acrylate monomer is to include propylene in molecule
The monomer of acid esters unit.
The mercaptan containing reactive hydrogen is alkylidene mercaptan or the aryl mercaptan containing active hydrogen-based, wherein containing work
Active hydrogen group can be hydroxyl or amido in the aryl mercaptan of property hydrogen.
Described (methyl) acryloyl monomer containing energy and reactive with active hydrogen is methacrylic chloride, acryloyl chloride, contains
There are the methacrylate of isocyanates or the acrylate containing isocyanates.
The polymerization inhibitor is hydroquinone, stannous chloride, phenthazine, p-hydroxyanisole, 2,6- di-t-butyls -4-
One or more in methylphenol, are preferably phenthazine or hydroquinone.
If the reactive hydrogen in the oligomer containing reactive hydrogen is amido, (methyl) acryloyl monomer reacted is containing different
The methacrylate of cyanate or the acrylate containing isocyanates, the then catalyst used are dibutyltindilaurylmercaptide cinnamic acid
Ester or tertiary amine；If the reactive hydrogen in the oligomer containing reactive hydrogen is hydroxyl, (methyl) acryloyl monomer reacted be containing
The methacrylate of isocyanates or the acrylate containing isocyanates, the then catalyst used are dibutyltindilaurylmercaptide osmanthus
Acid esters or tertiary amine；If the reactive hydrogen in the oligomer containing reactive hydrogen is hydroxyl, (methyl) acryloyl monomer reacted is first
Base acryloyl chloride or acryloyl chloride, the catalyst used are the tertiary amine catalysts such as triethylamine；
Polymerization described in the preparation process of macromonomer B is polymerisation in bulk or polymerisation in solution, preferably molten
Liquid polymerization；
If polymerization uses polymerisation in bulk in the preparation process of the oligomer containing reactive hydrogen, comprise the concrete steps that：In nitrogen
Under gas shielded, (methyl) acrylate monomer, polymerization initiator -5 and mercaptan containing reactive hydrogen are mixed, at 50~100 DEG C
When reaction 1~10 is small, the oligomer containing reactive hydrogen is obtained；Mercaptan and mole of (methyl) acrylate monomer containing reactive hydrogen
Than for 0.01~0.5:1, the mass ratio of polymerization initiator -5 and (methyl) acrylate monomer is 0.01~5:100.
The polymerization initiator -5 is all for water-soluble or oil-soluble polymerization initiator, the water soluble starter
Water soluble starter, the oil-soluble initiator are all oil-soluble initiators.
If polymerization uses polymerisation in solution in the preparation process of the oligomer containing reactive hydrogen, comprise the concrete steps that：In nitrogen
Under gas shielded, (methyl) acrylate monomer, polymerization initiator -6 and mercaptan containing reactive hydrogen are dissolved in solvent, 50~
When reaction 1~10 is small at 100 DEG C, the oligomer containing reactive hydrogen is obtained；Mercaptan and (methyl) acrylic ester list containing reactive hydrogen
The molar ratio of body is 0.01~0.5：1, the mass ratio of polymerization initiator -6 and (methyl) acrylate monomer is 0.01~5:
100；Solvent and the mass ratio of (methyl) acrylate monomer are 0.1~10：1.
The solvent is organic solvent or deionized water；Wherein organic solvent for benzene,toluene,xylene, tetrahydrofuran,
Methyl ethyl ketone, ethyl acetate or butyl acetate.
The polymerization initiator -6 is all for water-soluble or oil-soluble polymerization initiator, the water soluble starter
Water soluble starter, the oil-soluble initiator are all oil-soluble initiators.
A further object of the present invention is to provide a kind of application of the comb-shaped graft copolymer containing reactive group.
Comb-shaped graft copolymer of the present invention can be steady as the chain extender of polymer or blend polymer, bulking agent, hydrolysis
Agent, adhesive or sealant are determined, for the coating on timber, metal or plastics.
Additive of the comb-shaped graft copolymer of the present invention in an extruder as blend polymer can be used.The present invention
Comb-shaped graft copolymer is particularly suitable as the chain extender in biodegradable polymer and polymeric blends, bulking agent and
Hydrolysis stabilizer.
Comb-shaped graft copolymer of the present invention can be added in polymerization process or process other additives such as fire retardant,
It is surfactant, nucleator, coupling agent, filler, antioxidant, light stabilizer, bulking agent, inorganic filler, colouring agent, antistatic
Agent, dyestuff, pigment etc..
Beneficial effects of the present invention：
In accordance with the invention it is possible to the comb-shaped graft copolymer that a kind of side chain contains reactive group is obtained, reactive group therein
Group and complementation group, such as：Amido, carboxyl and hydroxyl have a very high reactivity, therefore can be with a variety of polyamide and poly-
The end group reaction of ester.Methacrylate ester monomer and multiple polymers (such as Kynoar (PVDF), styrene-acrylonitrile
Copolymer (SAN), acrylonitrile-butadiene-styrene terpolymer (ABS)) there is thermodynamic compatibility.Thus, synthesis
Reactive comb-shaped graft copolymer can be as the bulking agent of the incompatible co-mixing system of a variety of typical cases.
Meanwhile because reactive group can be reacted with the terminal hydroxy group or end carboxyl of polyester, which is also used as
Some are thermo-responsive, facile hydrolysis, the polyester material of melt strength difference and mechanical property deficiency, such as polylactic acid (PLA), poly- trimethylene carbon
The chain extender of acid esters (PPC), so as to improve processing and the application performance of material.
Preparation process of the present invention is simple, and molecule designability is strong, by rationally adjusting the length of main chain and side chain in molecule
With type, the parameter such as reactive group content, can obtain an optimal proportion, so as to be optimal different compatibilization effect；Use
It is convenient, reacting processing can be directly carried out in an extruder.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the reactive comb-shaped graft copolymer of gained in embodiment 2-2；
The stress-strain curve of polylactic acid/polyvinylidene fluoride alloy in Fig. 2 Application Examples 3-1.
Embodiment
The present invention is further analyzed with reference to specific embodiment.
It is the preparation process of macromonomer B first：
Embodiment 1-1
In a nitrogen atmosphere, by 90g methyl methacrylates (0.9mol), 10g glycidyl methacrylate
(0.07mol), 4g mercaptoethanols (0.05mol), 2.5g as polymerization initiator -6 4,4 '-azo two (4- cyano group amylalcohol)
Be uniformly mixed with 100g as the tetrahydrofuran of solvent, by temperature of reactor be raised to 70 DEG C reaction 5 it is small when.Then by reaction unit
0 DEG C is cooled to, by 10g triethylamines (0.1mol), 8g methacrylic chlorides (0.08mol) are added in reaction system, at 0 DEG C
4 hours are reacted, solvent is removed under reduced pressure, obtains macromonomer B, is denoted as M-2000 (E-0.1), the molecular weight of macromonomer B
For 2000, epoxy mass fraction is 10%.
Embodiment 1-2
In a nitrogen atmosphere, by 70g methyl methacrylates (0.7mol), 30g glycidyl methacrylate
(0.21mol), 3.6g mercaptoethanols (0.21mol), 2.4g as polymerization initiator -6 4,4 '-azo two (4- cyano group amylalcohol)
Be uniformly mixed with 100g as the tetrahydrofuran of solvent, by temperature of reactor be raised to 70 DEG C reaction 5 it is small when.Then by reaction unit
0 DEG C is cooled to, by 10g triethylamines (0.1mol), 8g methacrylic chlorides (0.08mol) are added in reaction system, at 0 DEG C
4 hours are reacted, solvent is then depressurized away, obtains macromonomer B, are denoted as M-2000 (E-0.3), point of macromonomer B
Son amount is 2000, and epoxy mass fraction is 30%.
Embodiment 1-3
In a nitrogen atmosphere, by 40g methyl methacrylates (0.4mol), 60g glycidyl methacrylate
(0.42mol), 3.2g mercaptoethanols (0.04mol), 1.9g as polymerization initiator -6 4,4 '-azo two (4- cyano group amylalcohol)
Be uniformly mixed with 100g as the tetrahydrofuran of solvent, by temperature of reactor be raised to 70 DEG C reaction 5 it is small when.Then by reaction unit
0 DEG C is cooled to, by 10g triethylamines (0.1mol), 8g methacrylic chlorides (0.08mol) are added in reaction system, at 0 DEG C
4 hours are reacted, solvent is then depressurized away, obtains macromonomer B, are denoted as M-2000 (E-0.6), point of macromonomer B
Son amount is 2000, and epoxy mass fraction is 60%.
Embodiment 1-4
Mercaptoethanol content in embodiment 1-2 as chain-transferring agent is substituted for 1.8 grams (0.02mol), will be used as and urge
The content of the triethylamine of agent is substituted for 4g (0.04mol), and methacrylic chloride is changed into 4.2g (0.04mol), other experiment bars
Part is consistent with embodiment 1-2, and macromonomer B is made, is denoted as M-6000 (E-0.3), the molecular weight of macromonomer B is
6000, epoxy mass fraction is 30%.
Embodiment 1-5
Mercaptoethanol content in embodiment 1-2 as chain-transferring agent is substituted for 1.3 grams (0.017mol), will be used as and urge
The content of the triethylamine of agent is substituted for 3g (0.03mol), and methacrylic chloride is changed into 3.1g (0.029mol), other experiment bars
Part is consistent with embodiment 1-2, and macromonomer B is made, is denoted as M-10000 (E-0.3), the molecular weight of macromonomer B is
10000, epoxy mass fraction is 30%.
Embodiment 1-6
In a nitrogen atmosphere, by 70g methyl methacrylates (0.7mol), 30g glycidyl methacrylate
(0.21mol), 3.6g mercaptoethanols (0.046mol), 4,4'- azo two (4- cyano group penta of the 2.4g as polymerization initiator -6
Alcohol) and 100g be uniformly mixed as the tetrahydrofuran of solvent, by temperature of reactor be raised to 70 DEG C reaction 5 it is small when.Then will reaction
System is cooled to 50 DEG C, adds 0.04 gram of (6.3*10 of dibutyl tin cinnamic acid ester as catalyst-5Mol), as polymerization inhibitor
0.06 gram of (5.5*10 of hydroquinone-4Mol), it is then that 11 grams of methylacryoyloxyethyl isocyanates (0.071mol) is slow
Slowly it is added in reaction system, when reaction 5 is small, solvent is removed under reduced pressure, obtains macromonomer B, molecular weight 2000, epoxy quality
Fraction is 30%.
Embodiment 1-7
In a nitrogen atmosphere, by 70g methyl methacrylates (0.7mol), 30g glycidyl methacrylate
(0.21mol), 3.6g mercaptoethanols (0.046mol), 1.6g as polymerization initiator -6 even 2,2'- nitrogen bis-isobutyronitrile and
100g is uniformly mixed as the tetrahydrofuran of solvent, by temperature of reactor be raised to 70 DEG C reaction 5 it is small when.Then by reaction unit
0 DEG C is cooled to, by 10g triethylamines (0.1mol), 8g methacrylic chlorides (0.08mol) are added in reaction system, at 0 DEG C
4 hours of lower reaction, solvent is then removed under reduced pressure, obtains macromonomer B, the molecular weight of macromonomer B is 2000, epoxy
Mass fraction is 30%.
Embodiment 1-8
In a nitrogen atmosphere, by 50g methyl methacrylates (0.5mol), 20g ethyl acrylates (0.2mol), 30g first
Base glycidyl acrylate (0.21mol), 3.6g mercaptoethanols (0.046mol), 2.4g as polymerization initiator -6 4,
4'- azos two (4- cyano group amylalcohol) and 100g are uniformly mixed as the tetrahydrofuran of solvent, and temperature of reactor is raised to 70 DEG C instead
Answer 5 it is small when.Then reaction unit is cooled to 0 DEG C, by 10g triethylamines (0.1mol), 8g methacrylic chlorides (0.08mol)
It is added in reaction system, 4 hours is reacted at 0 DEG C, solvent is then depressurized away, obtains macromonomer B, macromonomer
The molecular weight of B is 2000, and epoxy mass fraction is 30%.
Embodiment 1-9
In a nitrogen atmosphere, by 50g methyl methacrylates (0.5mol), 20g ethyl acrylates (0.2mol), 30g first
Base glycidyl acrylate (0.21mol), 3.6g mercaptoethanols (0.046mol), 2.4g as polymerization initiator -6 4,
4'- azos two (4- cyano group amylalcohol) and 100g are uniformly mixed as the tetrahydrofuran of solvent, and temperature of reactor is raised to 70 DEG C instead
Answer 5 it is small when.Then reaction unit is cooled to 0 DEG C, by 10g triethylamines (0.1mol), 8g methacrylic chlorides (0.08mol)
It is added in reaction system, 4 hours is reacted at 0 DEG C, solvent is then removed under reduced pressure, obtains macromonomer B, macromonomer
The molecular weight of B is 2000, and epoxy mass fraction is 30%.
Any macromonomer B being prepared using above-described embodiment prepares the comb shape graft copolymerization containing reactive group
Thing, embodiment are as follows：
Comb-shaped graft copolymer performance test methods containing reactive group are as follows：
(1) molecular weight determination of the comb-shaped graft copolymer containing reactive group
The comb-shaped graft copolymer of preparation is dissolved in chromatography pure tetrahydrofuran with the concentration of 2mg/ml, is oozed using gel
Saturating chromatography (GPC) measure number average molecular weight distribution, test temperature are 35 DEG C, and mobile phase is the chromatography pure tetrahydrofuran of 1ml/min.
Device：Waters 515
Chromatographic column：Splitter (the 10E5and 10E3 of two MZ-Gel SDplus, 10.0 μm of filler diameters)
Composition distribution：Optilab T-rEX detector
Calibration curve：2000 to 106g*mol-1Narrow distribution polystyrene standard specimen
(2) Molecular Structure of the comb-shaped graft copolymer containing reactive group
Using the molecular structure of comb-shaped graft copolymer of the Fourier transform infrared spectroscopy measure containing reactive group, 910cm-1
For epoxide group characteristic peak.
Device：Bruker, VERTEX 70V, scanning times 12 times, resolution ratio 2cm-1
Embodiment 2-1~2-16 prepares comb-shaped graft copolymer for solution polymerization process：
Embodiment 2-1
Under nitrogen protection, big point will be prepared in 100 grams of methyl methacrylates (MMA), 20 grams of embodiment 1-1
Sub- monomer B, 0.3 gram of 2,2 '-azodiisobutyronitrile (AIBN) and 0.2 gram of mercaptoethanol are added to 100 grams of toluene as solvent
Middle mixing and mechanical agitation 30 minutes, when the temperature of reactor is raised to reaction 5 is small at 70 DEG C, it is 22000 to obtain molecular weight
Comb-shaped graft copolymer containing reactive group.
Embodiment 2-2~2-8
With reference to embodiment 2-1, according to macromonomer B, the weight of methyl methacrylate (MMA) therebetween in table 1
Than change, while the monomer that macromonomer is changed into preparing in embodiment 1-9, other experiment conditions with embodiment 2-1 mono-
Cause, differential responses group content, different side chain lengths, the comb shape graft copolymerization containing reactive group of different side chain contents is made
Thing.
Each monomer composition ratio of 1 embodiment 2-1~2-8 of table
| Monomer composition | Monomer weight ratio | |
| Embodiment 2-1 | M-2000(E-0.1)/MMA | 2/8 |
| Embodiment 2-2 | M-2000(E-0.3)/MMA | 2/8 |
| Embodiment 2-3 | M-2000(E-0.6)/MMA | 2/8 |
| Embodiment 2-4 | M-6000(E-0.3)/MMA | 2/8 |
| Embodiment 2-5 | M-10000(E-0.3)/MMA | 2/8 |
| Embodiment 2-6 | M-2000(E-0.1)/MMA | 1/9 |
| Embodiment 2-7 | M-2000(E-0.6)/MMA | 5/5 |
| Embodiment 2-8 | M-10000(E-0.3)/MMA | 4/6 |
Embodiment 2-9
By 2 in embodiment 2-1,2 '-azodiisobutyronitrile (AIBN) is substituted for dibenzoyl peroxide, and mercaptoethanol is replaced
For lauryl mercaptan, other experiment conditions are consistent with embodiment 2-1, and the comb-shaped graft copolymer containing reactive group is made.
Embodiment 2-10
Under nitrogen protection, big point will prepared in 2 grams of benzoyl peroxides, 1 gram of thioacetic acid, 70 grams of embodiment 1-1
Sub- monomer B, 30 grams methyl methacrylate is dissolved in 200 grams of methyl ethyl ketone, at 70 DEG C react 8 it is small when, be made contain reactive group
Comb-shaped graft copolymer.
Embodiment 2-11~2-16
Methyl ethyl ketone in embodiment 2-10 is replaced and changes ethyl acetate, butyl acetate, propane diols, dipropylene glycol list into successively
Methyl ether, dipropylene glycol, other experiment conditions are identical with embodiment 2-10, and the comb shape graft copolymerization containing reactive group is made
Thing.
Embodiment 2-17~2-21 prepares the comb-shaped graft copolymer containing reactive group for suspension polymerization：
Embodiment 2-17
By 0.3 gram of 2,2 '-azodiisobutyronitrile (AIBN), 0.1 gram of 3- mercaprol, 70 grams of methyl methacrylates, 30
The macromonomer B prepared in gram embodiment 1-1 is uniformly mixed, and obtains monomer mixture.1.5 grams of sodium dihydrogen phosphates are dissolved in
Add 2 grams of polyvinylpyrrolidones in 300 grams of deionized waters thereto at the same time.Monomer mixture is added in above-mentioned solution, machine
Tool stirs evenly, while with nitrogen purge.Reaction at 65 DEG C carry out 4 it is small when after, reaction product is filtered, washing and
Drying and dehydrating obtains the comb-shaped graft copolymer containing reactive group that number-average molecular weight is 24000.
Embodiment 2-18
Under nitrogen protection, what will be prepared in the macromonomer B prepared in 60 grams of embodiment 1-1,40 grams of embodiments 1 divides greatly
Sub- monomer B and 0.1 gram of isooctyl thioglycolate.1 gram of disodium-hydrogen is dissolved in 1000 grams of deionized waters while thereto
Add 2 grams of polyvinyl alcohol.Monomer mixture is added in above-mentioned solution, mechanical agitation is uniform, while with nitrogen purge,
Then 0.01 gram of K is added2S2O8-FeSO4, when reaction 10 is small at 40 DEG C, reaction product is filtered, washing and drying and dehydrating obtain
Comb-shaped graft copolymer containing reactive group.
Embodiment 2-19
Nitrogen protection under, by the macromonomer B prepared in 50 grams of embodiment 1-1,50 grams of butyl methacrylates and
0.2 gram of glycol dimercaptosuccinate is uniformly mixed.0.1 gram of dodecyl sodium sulfate and 2 grams of Gelatins are gone in 300 grams
In ionized water.Monomer mixture is added in above-mentioned solution, mechanical agitation is uniform, while with nitrogen purge, Ran Houjia
Enter double (the 2- methyl-props amidine) dihydrochlorides of 2 grams of 2,2'- azos, when reaction 1 is small at 80 DEG C, reaction product is filtered, washes and does
Dry dehydration obtains the comb-shaped graft copolymer containing reactive group.
Embodiment 2-20
Under nitrogen protection, by 0.3 gram 2, the macromolecular that is prepared in 2 '-azodiisobutyronitrile (AIBN), 40 grams of embodiment 1-1
Monomer B, 60 grams of methyl methacrylates and 1 gram of 3- mercaptopropionic acid N-butyl are uniformly mixed.By 2 grams of alkali calcium phosphate and 0.03
Gram neopelex is dissolved in 200 grams of deionized waters.Monomer mixture is added in above-mentioned solution, mechanical agitation is equal
It is even, while with nitrogen purge, when reaction 5 is small at 60 DEG C, reaction product is filtered, washing and drying and dehydrating are obtained containing anti-
Answer the comb-shaped graft copolymer of group.
Embodiment 2-21
Under nitrogen protection, by 0.1 gram 2,2 '-azodiisobutyronitrile (AIBN), 1 gram of isooctyl thioglycolate, 20 grams of implementations
Example 1-1 in prepare macromonomer B, 80 grams of methyl methacrylates and be uniformly mixed.By 1 gram of hydroxypropyl methyl cellulose and
0.01 gram of cetyl trimethylammonium bromide is dissolved in 100 grams of deionized waters.Monomer mixture is added in above-mentioned solution, machine
Tool stirs evenly, while with nitrogen purge, when reaction 5 is small at 60 DEG C, reaction product is filtered, washing and drying and dehydrating
Obtain the comb-shaped graft copolymer containing reactive group.
Embodiment 2-22~embodiment 2-24 prepares the comb-shaped graft copolymer containing reactive group using emulsion polymerization：
Embodiment 2-22
Under nitrogen protection, 0.4 gram of emulsifying agent TWEEN-80 and 200 grams of deionized waters are sequentially added in reaction unit, so
Afterwards by the mixed of the macromonomer B prepared in 90 grams of methyl methacrylates, 10 grams of embodiment 1-1 and 0.3 gram of Thiomalic acid
Close and emulsified in liquid addition reactor, be eventually adding 0.2 gram of K2S2O8-FeSO4, react carried out at 65 DEG C 4 it is small when, it is equal to obtain number
Molecular weight is 23000 comb-shaped graft copolymer containing reactive group.
Embodiment 2-23
Under nitrogen protection, after 2 grams of dodecyl trimethyl ammonium bromide are dispersed in 1 kilogram of deionized water, Ran Houjia
Enter the mixing of the macromonomer B and 0.2 gram of Thiomalic acid that are prepared in 80 grams of methyl methacrylates, 20 grams of embodiment 1-1
Liquid emulsifies in deionized water, after being passed through nitrogen, adds 0.2 gram of K2S2O8-FeSO4, when reaction 10 is small at 40 DEG C, obtain containing anti-
Answer the comb-shaped graft copolymer of group.
Embodiment 2-24
Under nitrogen protection, after 10 grams of lauryl sodium sulfate are dispersed in 300 grams of deionized waters, then sequentially add
The mixed liquor of the macromonomer B, 80 grams of methyl methacrylates and the 0.5 gram of mercaptoethanol that are prepared in 20 grams of embodiment 1-1 exists
Emulsify in deionized water, last 5 gram 2,2 '-azo diisobutyl amidine dihydrochloride, when reaction 1 is small at 80 DEG C, obtain containing anti-
Answer the comb-shaped graft copolymer of group.
Embodiment 2-25~2-26 prepares the comb-shaped graft copolymer containing reactive group for mass polymerization：
Embodiment 2-25
Under nitrogen protection, by 0.001 gram 2,2 '-azodiisobutyronitrile (AIBN), 0.003 gram of mercaptoethanol, 0.1 gram big point
Sub- monomer B, 99.9 grams of methyl methacrylates are uniformly mixed, and when reaction 3 is small at 50 DEG C, obtain the comb shape grafting containing reactive group
Copolymer.
Embodiment 2-26
Under nitrogen protection, by 0.001 gram 2,2 '-azodiisobutyronitrile (AIBN), 0.002 gram of lauryl mercaptan, 40
Macromonomer B, 10 grams of ethyl acrylates and the 50 grams of methyl methacrylates prepared in gram embodiment 1-1 are uniformly mixed, and 90
When reaction 1 is small at DEG C, the comb-shaped graft copolymer containing reactive group is obtained.
Fig. 1 is the infrared spectrogram of the reactive comb-shaped graft copolymer of gained in embodiment 2-2；
910cm-1Position is the eigen vibration peak of epoxide group, this demonstrate that the reactive comb-shaped graft copolymer
Side chain contains epoxide group.
It is the preparation of polylactic acid/Kynoar (PLLA/PVDF) alloy below：
The load-deformation curve of polylactic acid/Kynoar (PLLA/PVDF) alloy according to JIS-K7113 standard testings,
5966 types of stretching-machine model Instron.
Application Example 3-1：
By the comb-shaped graft copolymer of the invention containing reactive group in embodiment 2-2, PLLA, PVDF are according to 2 ratio of table
It is added in mixer (HAAKE Polylab QC) and is mixed, is kneaded 10 minutes under 190 degrees Celsius, 50 turns of rotor speed/
Minute.
Application Example 3-2：
As shown in table 2, PVDF inventorys are changed into 35 grams, PLLA is changed into by other conditions according to Application Example 3-1
15 grams.
Application Example 3-3：
As shown in table 2, PVDF inventorys are changed into 15 grams, PLLA is changed into by other conditions according to Application Example 3-1
35 grams.
The formula and material property table of 2 Application Example 1~3 of table
Comparative example：Shown in table 3, other conditions do not add the present invention containing reaction according to Application Example 3-1
The graft copolymer of group.
The formula and material property table of 3 comparative example of table
Shown in table 2,3, add the 3wt ﹪ graft copolymers of the present invention relative to PLLA and PVDF gross masses as increase-volume
After agent, the elongation at break of PLLA/PVDF alloys can be significantly improved, it is a kind of efficient to illustrate comb-shaped graft copolymer of the present invention
Bulking agent.
Fig. 2 is the stress-strain curve of polylactic acid/polyvinylidene fluoride alloy in Application Example 3-1.
This demonstrate that the addition of the reactive comb shape molecule drastically increases polylactic acid/polyvinylidene fluoride alloy material
The mechanical property of material.
It is that the present invention is not limited only to above-described embodiment, as long as meeting for limitation of the invention that above-described embodiment, which is not,
Application claims, belong to protection scope of the present invention.
Claims (10)
1. a kind of comb-shaped graft copolymer containing reactive group, it is characterised in that the copolymer is that main chain is small molecule monomer A, side
Chain is the comb-shaped graft copolymer of macromonomer B；The weight of macromonomer B is comb-shaped graft copolymer quality
The weight of 0.1wt ﹪~80wt ﹪, small molecule monomer A are 99.9wt ﹪~20wt ﹪ of comb-shaped graft copolymer quality；
The number-average molecular weight of the comb-shaped graft copolymer is 5000~100000；
The macromonomer B is represented with general formula (1)：
Wherein R1、R2For hydrogen atom or methyl, R3For glycidyl, R4For hydrogen atom or sec-butyl, X expressions-CH2CH(OH)
CH2- or-Z-NHCO-, Y be-L1-L2- S-, Z are-(CH2CH2O)a(CH2)b-,L1For Direct Bonding ,-O- ,-COO- or-
NH-,L2For C1~C20 alkylidenes or C6~C20 arlydene, S represents sulphur atom, and n is 5~100 integer, and m is 0 or 1, a
For 0~20 integer, b is 1~20 integer；
The number-average molecular weight of the macromonomer B is 500~10000；
The small molecule monomer A is methacrylate, acrylate, Methacrylamide, unsaturated nitrile, styrene monomer
And its one or more of derivative.
2. a kind of comb-shaped graft copolymer containing reactive group as claimed in claim 1, it is characterised in that small molecule monomer A's
Weight is 80wt ﹪~50wt ﹪ of comb-shaped graft copolymer quality；The weight of macromonomer B is comb-shaped graft copolymer matter
5wt ﹪~50wt ﹪ of amount；The number-average molecular weight of comb-shaped graft copolymer is 15000~60000.
3. prepare a kind of method of the comb-shaped graft copolymer containing reactive group as claimed in claim 1, it is characterised in that should
Method be small molecule monomer A and macromonomer B are copolymerized to be formed main chain be small molecule monomer A, side chain be macromonomer B
Comb-shaped graft copolymer；The addition of macromonomer B for comb-shaped graft copolymer quality 0.1wt ﹪~80wt ﹪, small point
The addition of sub- monomer A is 99.9wt ﹪~20wt ﹪ of comb-shaped graft copolymer quality；
The number-average molecular weight of the comb-shaped graft copolymer is 5000~100000；
The small molecule monomer A is methacrylate, acrylate, Methacrylamide, unsaturated nitrile, styrene monomer
And its one or more of derivative.
A kind of 4. preparation method of the comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterised in that institute
The copolymerization process stated is polymerisation in bulk, and concrete operations are under nitrogen protection, by polymerization initiator -1, chain-transferring agent, small molecule
Monomer A, macromonomer B are mixed, and when reaction 1~10 is small at 50~120 DEG C, obtain comb-shaped graft copolymer；
The polymerization initiator -1 is oil-soluble initiator；
The chain-transferring agent is lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid, sulfydryl
2-ethyl hexyl ethanoate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate；
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Polymerization triggers
Agent -1 and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.001~5：100；Chain-transferring agent triggers with polymerizeing
The molar ratio of agent -1 is 0.1~10：1.
A kind of 5. preparation method of the comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterised in that institute
The copolymerization process stated is solution polymerization process, concrete operations be under nitrogen protection, by polymerization initiator -2, chain-transferring agent, small point
Sub- monomer A, macromonomer B are dissolved in organic solvent, when reaction 1~10 is small at 50~120 DEG C；
The polymerization initiator -2 is water-soluble or oil-soluble initiator；
The chain-transferring agent is lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid, sulfydryl
2-ethyl hexyl ethanoate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate；
The organic solvent for benzene,toluene,xylene, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, butyl acetate, propane diols,
Dipropylene glycol methyl ether or dipropylene glycol；
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Polymerization triggers
Agent -2 and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.001~5：100；Chain-transferring agent triggers with polymerizeing
The molar ratio of agent -2 is 0.1~10：1；Organic solvent and macromonomer B and the mass ratio of small molecule monomer A total amounts for 0.5~
5:1。
A kind of 6. preparation method of the comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterised in that institute
The copolymerization process stated is suspension polymerization, concrete operations be under nitrogen protection, by polymerization initiator -3, chain-transferring agent, small point
Sub- monomer A, macromonomer B are mixed, be scattered under mechanical stirring dissolved with suspension stabilizer and suspension stabilization aid go from
In sub- water, when reaction 1~10 is small at 40~80 DEG C；
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Chain-transferring agent with
The molar ratio of polymerization initiator -3 is 0.1~10：1；Deionized water and small molecule monomer A and the quality of macromonomer B total amounts
Than for 0.5~10:1；Suspension stabilizer and the mass ratio of deionized water are 0.001~0.05:1；Suspension stabilizer and small molecule
Monomer A and the mass ratio of macromonomer B total amounts are 0.001~0.05:1；The quality of suspension stabilizer and suspension stabilization aid
Than for 1~500:1；Polymerization initiator -3 and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.001~5：
100；
The polymerization initiator -3 is oil-soluble initiator；
The chain-transferring agent is lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid, sulfydryl
2-ethyl hexyl ethanoate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate；
The suspension stabilizer is organic suspending agent, the one or two of Inorganic suspending agent；
The suspension stabilization aid is disodium-hydrogen, sodium dihydrogen phosphate, sodium sulphate, sodium chloride, cetyl trimethyl bromine
Change the one or more in ammonium, neopelex, dodecyl sodium sulfate, lauryl sodium sulfate.
A kind of 7. preparation method of the comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterised in that institute
The copolymerization process stated is emulsion polymerization, and concrete operations are after emulsifying agent is dispersed in deionized water, then to add small molecule
The mixed liquor of monomer A, macromonomer B and chain-transferring agent, small molecule monomer A, macromonomer B are emulsified in deionized water,
It is passed through after nitrogen when adding that reaction 1~10 is small at polymerization initiator -4,40~80 DEG C, obtains comb-shaped graft copolymer；
Macromonomer B and small molecule monomer A and the mass ratio of macromonomer B total amounts are 0.1~80：100；Emulsifying agent is with going
The mass ratio of ionized water is 0.001~0.05:1；The matter of polymerization initiator -4 and small molecule monomer A and macromonomer B total amounts
Amount is than being 0.001~5：100；The molar ratio of chain-transferring agent and polymerization initiator -4 is 0.1~10：1；Emulsifying agent and small molecule list
Body A and the mass ratio of macromonomer B total amounts are 0.001~0.1：1；
The polymerization initiator -4 is water soluble starter；
The chain-transferring agent is lauryl mercaptan, mercaptoethanol, 3- mercaprols, thioacetic acid, Thiomalic acid, sulfydryl
2-ethyl hexyl ethanoate, 3- mercaptopropionic acids N-butyl or glycol dimercaptosuccinate；
The emulsifying agent is cationic, anionic or non-ionic emulsifying agent.
A kind of 8. preparation method of the comb-shaped graft copolymer containing reactive group as claimed in claim 3, it is characterised in that institute
The preparation method of the macromonomer B stated is：Using the mercaptan containing reactive hydrogen as chain-transferring agent, gathered using Raolical polymerizable
(methyl) acrylate monomer is closed, obtains the oligomer containing reactive hydrogen；Then by obtained oligomer in catalyst and inhibition
Under the conditions of agent is existing, reacted with (methyl) acryloyl monomer containing energy and reactive with active hydrogen, 1~10 is reacted at 0~100 DEG C
Hour, obtain macromonomer B；
The molar ratio of the mercaptan containing reactive hydrogen and (methyl) acrylate monomer is 0.01~0.5：1；Polymerization inhibitor
Molar ratio with the oligomer containing reactive hydrogen is 0.001~0.1:1；The molar ratio of catalyst and the oligomer containing reactive hydrogen is
0.001~0.1:1；Oligomer and the molar ratio of energy and (methyl) acryloyl monomer of reactive with active hydrogen containing reactive hydrogen are 0.3
~1:1；
Described (methyl) acrylate monomer is methacrylate ester monomer or acrylate monomer；Methacrylic acid
Ester system monomer is the monomer for including methacrylate unit in molecule, and acrylate monomer is to include acrylate in molecule
The monomer of unit；
The mercaptan containing reactive hydrogen is the aryl mercaptan containing active hydrogen-based, wherein in the aryl mercaptan containing reactive hydrogen
Active hydrogen group is hydroxyl or amido；
Described (methyl) acryloyl monomer containing energy and reactive with active hydrogen is methacrylic chloride, acryloyl chloride, containing different
The methacrylate of cyanate or the acrylate containing isocyanates；
The polymerization inhibitor is hydroquinone, stannous chloride, phenthazine, p-hydroxyanisole, 2,6- di-t-butyl -4- methylbenzenes
One or more in phenol；
If the reactive hydrogen in the oligomer containing reactive hydrogen is amido, (methyl) acryloyl monomer reacted is to contain isocyanic acid
The methacrylate of ester or the acrylate containing isocyanates, then the catalyst used for dibutyltin dilaurate or
Tertiary amine；If the reactive hydrogen in the oligomer containing reactive hydrogen is hydroxyl, (methyl) acryloyl monomer reacted is to contain isocyanide
The methacrylate of acid esters or the acrylate containing isocyanates, the then catalyst used are dibutyltin dilaurate
Or tertiary amine；If the reactive hydrogen in the oligomer containing reactive hydrogen is hydroxyl, (methyl) acryloyl monomer reacted is methyl-prop
Alkene acyl chlorides or acryloyl chloride, the catalyst used are tertiary amine.
A kind of 9. preparation method of the comb-shaped graft copolymer containing reactive group as claimed in claim 8, it is characterised in that institute
The molar ratio of the mercaptan containing reactive hydrogen stated and (methyl) acrylate monomer is 0.01~0.3：1；The polymerization inhibitor
For phenthazine or hydroquinone.
A kind of 10. comb-shaped graft copolymer containing reactive group as claimed in claim 1 or 2, as polymer or polymerization
Chain extender, bulking agent, hydrolysis stabilizer, adhesive or the sealant of thing blend, for the painting on timber, metal or plastics
The application of layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410816060.0A CN104610515B (en) | 2014-12-24 | 2014-12-24 | A kind of comb-shaped graft copolymer containing reactive group and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410816060.0A CN104610515B (en) | 2014-12-24 | 2014-12-24 | A kind of comb-shaped graft copolymer containing reactive group and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104610515A CN104610515A (en) | 2015-05-13 |
| CN104610515B true CN104610515B (en) | 2018-04-20 |
Family
ID=53145185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410816060.0A Active CN104610515B (en) | 2014-12-24 | 2014-12-24 | A kind of comb-shaped graft copolymer containing reactive group and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104610515B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239235B (en) * | 2016-12-27 | 2019-11-19 | 金发科技股份有限公司 | A kind of graft copolymer and its application containing reactive group |
| CN108239241B (en) * | 2016-12-27 | 2020-03-13 | 金发科技股份有限公司 | Graft copolymer containing isocyanate group and application thereof |
| CN108239242B (en) * | 2016-12-27 | 2020-03-13 | 金发科技股份有限公司 | Graft copolymer containing acid anhydride group and application thereof |
| CN108239234B (en) * | 2016-12-27 | 2019-11-19 | 金发科技股份有限公司 | A kind of graft copolymer and its application containing epoxy group |
| US10682837B2 (en) * | 2017-06-09 | 2020-06-16 | The Proctor & Gamble Company | Method and compositions for applying a material onto articles |
| CN107383799B (en) * | 2017-07-27 | 2019-12-27 | 杭州福膜新材料科技股份有限公司 | Special material for polybutylene terephthalate-polyvinylidene fluoride alloy |
| CN108359061B (en) * | 2018-02-12 | 2020-06-30 | 金发科技股份有限公司 | Graft copolymer containing acid anhydride group and preparation method and application thereof |
| CN108314761A (en) * | 2018-02-12 | 2018-07-24 | 金发科技股份有限公司 | A kind of graft copolymer and its preparation method and application containing reactive group |
| CN108409922B (en) * | 2018-02-12 | 2020-07-21 | 金发科技股份有限公司 | Graft copolymer containing reactive group and preparation method and application thereof |
| CN108359060B (en) * | 2018-02-12 | 2020-06-30 | 金发科技股份有限公司 | Graft copolymer containing reactive group and preparation method and application thereof |
| CN108440725B (en) * | 2018-02-12 | 2020-07-24 | 金发科技股份有限公司 | Epoxy group-containing graft copolymer and preparation method and application thereof |
| CN108409912B (en) * | 2018-02-12 | 2020-07-24 | 金发科技股份有限公司 | Epoxy group-containing graft copolymer and preparation method and application thereof |
| CN110330659B (en) * | 2019-07-26 | 2022-06-17 | 杭州师范大学 | Splicing comb type reactive copolymer containing reactive group and preparation method and application thereof |
| CN111849139A (en) * | 2020-08-11 | 2020-10-30 | 杭州师范大学 | High-strength and high-toughness fully biodegradable material and preparation method thereof |
| CN112280079A (en) * | 2020-09-23 | 2021-01-29 | 南阳市星光数码材料有限公司 | Quick-drying type light diffusion back-blowing lamp box piece and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
| CN102040711A (en) * | 2010-11-09 | 2011-05-04 | 华南理工大学 | Amphiphilic polymer pigment wetting dispersant for water-based coating and preparation method thereof |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7795347B2 (en) * | 2003-03-14 | 2010-09-14 | Mitsui Chemicals, Inc. | Multi-branched polymer, process for producing the same, and applications thereof |
-
2014
- 2014-12-24 CN CN201410816060.0A patent/CN104610515B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
| CN102040711A (en) * | 2010-11-09 | 2011-05-04 | 华南理工大学 | Amphiphilic polymer pigment wetting dispersant for water-based coating and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104610515A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104610515B (en) | A kind of comb-shaped graft copolymer containing reactive group and preparation method and application | |
| Hilburg et al. | A universal route towards thermoplastic lignin composites with improved mechanical properties | |
| CN103421154B (en) | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof | |
| AU627419B1 (en) | Process for preparing stabilized polymer dispersion | |
| CA2233621C (en) | Seed polymerized latex polymer having a gradient polymeric morphology and process for preparing the same | |
| EP2513174B1 (en) | Emulsion polymerization of esters of itaconic acid | |
| Guyot | Recent progress in reactive surfactants in emulsion polymerisation | |
| Song et al. | Convenient synthesis of thermo‐responsive PtBA‐g‐PPEGMEMA well‐defined amphiphilic graft copolymer without polymeric functional group transformation | |
| CN105482342B (en) | Excellent vinyl chloride resin of cryogenic property and preparation method thereof | |
| EP3572439A1 (en) | Rubbery polymer, graft copolymer and thermoplastic resin composition | |
| WO2015090657A1 (en) | Process for the preparation of polymers based on vinyl halides | |
| CN100554297C (en) | The method for preparing vinyl aromatic (being total to) polymkeric substance that is grafted on the elastomerics in the mode of control | |
| CN114133500B (en) | Triblock copolymer tough resin latex and preparation method thereof | |
| CN107082984A (en) | Nano-particle latex and nano particle reinforced tenacity increased vinyl chloride compound resin and preparation method thereof | |
| CN109971156A (en) | A kind of acrylic ester modified water-soluble polyurethane lotion and preparation method thereof | |
| CN112513113B (en) | Graft copolymer, thermoplastic resin composition, and molded article thereof | |
| Picchio et al. | New strategy to improve acrylic/casein compatibilization in waterborne hybrid nanoparticles | |
| Li et al. | Well‐defined amphiphilic graft copolymer consisting of hydrophilic poly (acrylic acid) backbone and hydrophobic poly (vinyl acetate) side chains | |
| CN109679038A (en) | Emulsion polymerisation system, emulsion polymerisation process and application | |
| CA2379418C (en) | Method for producing aqueous resin dispersion composition | |
| DE4302552A1 (en) | Graft and core-shell copolymers with improved phase connection between the graft base and the grafted-on polymer phase | |
| CN209383683U (en) | Emulsion polymerisation system | |
| Borisova et al. | Synthesis of amphiphilic block-gradient copolymers of styrene and acrylic acid by Nitroxide Mediated Polymerization | |
| Lee | The control of structure in emulsion polymerization | |
| EP0528806A1 (en) | Ethylene vinyl silane copolymer and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |