CN106519144A - Vinyl grafted copolymer, resin composite containing same and preparation method of vinyl grafted copolymer - Google Patents
Vinyl grafted copolymer, resin composite containing same and preparation method of vinyl grafted copolymer Download PDFInfo
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- CN106519144A CN106519144A CN201610789392.3A CN201610789392A CN106519144A CN 106519144 A CN106519144 A CN 106519144A CN 201610789392 A CN201610789392 A CN 201610789392A CN 106519144 A CN106519144 A CN 106519144A
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/10—Esters
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C08L27/00—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention relates to a preparation method a vinyl grafted copolymer. The preparation method comprises the following steps: agglomerating polysiloxane latex under the existence of the polysiloxane latex and a vinyl monomer (b1), and meanwhile, carrying out free radical polymerization on the vinyl monomer (b1) and the polysiloxane latex, thus obtaining agglomerate; grafting and polymerizing the obtained agglomerate with a vinyl monomer (b2), thus obtaining the vinyl grafted copolymer, wherein the vinyl monomer (b1) and the vinyl monomer (b2) can be identical and can also be different. According to the preparation method disclosed by the invention, the vinyl grafted copolymer of a multilayered structure can be obtained, the vinyl grafted copolymer can be used as an impact modifier, and a resin composite having both excellent low temperature impact resistance and excellent flame resistance can be obtained by adding the vinyl grafted copolymer in thermoplastic resin.
Description
Technical field
The present invention relates to a kind of preparation method of ethene base system graft copolymer, the ethene base system obtained by the preparation method
Graft copolymer and the resin combination containing the ethene base system graft copolymer.
Background technology
Thermoplastic resin molded article is widely used in the every field of daily life, but generally goes through modified
Can have good impact resistance and anti-flammability.The conventional toughener of addition, such as MBS, ACR, EVA-g-MAH etc., can give
The good impact flexibility of thermoplastic resin, but while can also cause the decline of anti-flammability.And add conventional fire retardant for example low
Polyphosphoric acid ester type compound, can play good flame retardant effect, but and can reduce impact resistance.Therefore have fire-retardant and toughness reinforcing concurrently
The developmental research of the anti-impact modifier of effect increasingly has using value.
Although in addition, many materials have excellent impact resistance at normal temperatures, at low ambient temperatures, all existing resistance to tired
Labor low intensity, the high shortcoming of stress cracking and notch shock susceptibility is also easy to produce, these all limit their application.Improve this
The low-temperature flexibility of a little materials, expands its range of application and also has very much realistic meaning.
There is polysiloxanes lower temperature resistance, low-surface-energy, resistance to water, resistance to ag(e)ing, corrosion resistance and weatherability etc. to be
The excellent and unique performance of row, and due to containing element silicon in structure so as to certain flame retardant effect.At present, patent
Document 1 discloses a kind of impact resistance for adding polysiloxanes based polymer to improve resin, and which is still kept at high temperature
The method of good toughness.But polysiloxanes based polymer is with the compatibility of many thermoplastic resins and bad, and alkene
Polymer and thermoplastic resin have a good compatibility, and due to molecular backbone be the carbon-to-carbon bond structure of saturation, side chain be pole
Property ester group and there is the characteristics such as excellent weatherability, oil resistivity, ozone resistance and uvioresistant.Make polysiloxanes and vinyl list
Body glycerol polymerization, it is possible to increase polysiloxanes and the compatibility of polymeric matrix, makes elastic granule more fully be distributed in resin
In matrix.
In addition, for comprehensive polysiloxanes and the advantage of polyacrylate, patent document 2 discloses that both are gathered by one kind
After each self-crosslinking of compound, the network structure of gained is continuously mutually interted, is added in material to be changed by the mixture for obtaining
The method of property.Patent document 3 discloses that a kind of by the macromonomer formed by polysiloxanes and diisocyanate and propylene
The method of esters of gallic acid monomer copolymerization.Patent document 4 discloses that a kind of by poly organo methane series rubber and vinyl monomer-grafted
The method of copolymerization.
Prior art literature
Patent document
Patent document 1：US4826929(A)
Patent document 2：US5424375(A)
Patent document 3：US6545114(B1)
Patent document 4：CN103391952(A)
The content of the invention
Invent problem to be solved
But, in technology disclosed in above-mentioned document, also fail to for polysiloxanes and vinyl monomer to be copolymerized into compatibility
Well, the excellent composite of impact resistance of the combination property especially under anti-flammability and cryogenic conditions.
In view of the above fact, problem of the invention is：There is provided one kind can be by polysiloxanes and vinyl monomer copolymerization
Into compatibility it is good, have anti-flammability and cryogenic conditions concurrently under impact resistance graft copolymer method, and provide by this
Ethene base system graft copolymer and the resin combination containing the ethene base system graft copolymer that method is obtained.
For solving the scheme of problem
As a result the present inventor is had found through a series of researchs, by making agglomeration and the vinyl list of polysiloxane series latex
The radical polymerization of body is carried out simultaneously, and makes the agglomerate for obtaining be polymerized with vinyl monomer-grafted, is obtained ethene base system and is connect
Graft copolymer, thus prepare that a kind of compatibility is good, have anti-flammability and cryogenic conditions concurrently under the ethene base system of impact resistance connect
Graft copolymer.And it was found that by the control to agglomerate particle size and the optimization to vinyl monomer ratio, further can carry
Impact resistance under the anti-flammability and cryogenic conditions of high-vinyl system graft copolymer.
A first aspect of the present invention provides a kind of preparation method of ethene base system graft copolymer, and which includes：In poly- silica
In the presence of methane series latex and vinyl monomer (b1), by polysiloxane series latex agglomeration, at the same make vinyl monomer (b1) with
Polysiloxane series latex radical polymerization, the step of obtain agglomerate；Connect with vinyl monomer (b2) with the agglomerate for making to obtain
Branch polymerization, the step of obtain ethene base system graft copolymer, wherein, vinyl monomer (b1) and (b2) can with it is identical can not also
Together.
Also, in the first aspect, above-mentioned polysiloxane series latex is the glue of the straight chain type polysiloxanes with vinyl
Breast, the contents of ethylene in above-mentioned polysiloxane series latex is relative to 100 matter of solid constituent in above-mentioned polysiloxane series latex
Amount % is 0.01～3 mass %.
Also, in the first aspect, above-mentioned polysiloxane series latex is by making dimethyl silica alkanes monomer, vinyl silicon
Oxygen alkanes monomer and the polymerization of closure agent as needed are obtained, and in the manufacture of above-mentioned polysiloxane series latex do not use crosslinking
Agent, the number-average molecular weight (Mn) of above-mentioned polysiloxane series latex is 200,000～600,000.
Also, in the first aspect, before agglomeration polysiloxane series latex average grain diameter be 20～80nm, poly- silicon after agglomeration
The average grain diameter of oxygen methane series latex is 100～800nm.
Also, addition in the first aspect, by above-mentioned polysiloxane series latex in terms of solid constituent, above-mentioned vinyl
When the addition of the addition and above-mentioned vinyl monomer (b2) of monomer (b1) total is set to 100 mass parts, above-mentioned poly- silica
The addition that methane series latex is counted with solid constituent as 20～40 mass parts, above-mentioned vinyl monomer (b1) and above-mentioned vinyl monomer
(b2) total addition is 60～80 mass parts.
Also, addition in the first aspect, by above-mentioned polysiloxane series latex in terms of solid constituent, above-mentioned vinyl
When the addition of the addition and above-mentioned vinyl monomer (b2) of monomer (b1) total is set to 100 mass parts, above-mentioned vinyl
The addition of monomer (b1) is 20～60 mass parts, and the addition of above-mentioned vinyl monomer (b2) is 20～40 mass parts.
Also, in the first aspect, above-mentioned vinyl monomer (b1) and above-mentioned vinyl monomer (b2) are selected from (methyl) third
E pioic acid methyl ester, (methyl) ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) n-butyl acrylate, (methyl) propylene
Acid, (methyl) Isooctyl acrylate monomer, (methyl) acrylonitrile, N hydroxymethyl acrylamide, styrene and the different ice of (methyl) acrylic acid
More than a kind in piece ester.
In addition, a second aspect of the present invention provides vinyl obtained from a kind of preparation method by described in first aspect
It is graft copolymer, the butanone insoluble component of the ethene base system graft copolymer is more than 80 mass %.
Also, in second aspect, the number-average molecular weight of the butanone soluble ingredient of above-mentioned ethene base system graft copolymer
(Mn) it is 10000～140000, the ratio (Mw/Mn) of weight average molecular weight (Mw) and number-average molecular weight (Mn) is 2.0～3.0.
A third aspect of the present invention provides a kind of resin combination, and the ethene base system grafting which contains described in second aspect is common
Polymers and thermoplastic resin.
Invention effect
In accordance with the invention it is possible to provide a kind of preparation method of ethene base system graft copolymer, the preparation method can be by
Polysiloxanes and vinyl monomer be copolymerized into that compatibility is good, have anti-flammability and cryogenic conditions concurrently under impact resistance vinyl
It is graft copolymer.And the thermoplastic resins such as the ethene base system graft copolymer obtained by above-mentioned preparation method and PC are mixed
When, all excellent resin combination of low-temperature impact resistance and anti-flammability can be obtained.The resin combination of the present invention can be extensive
For electronic apparatus and industrial machinery part.
Specific embodiment
First, the preparation method of the ethene base system graft copolymer of the present invention is illustrated.
The preparation method of the ethene base system graft copolymer of the present invention includes：In polysiloxane series latex and vinyl monomer
(b1) in the presence of, while by polysiloxane series latex agglomeration, while making vinyl monomer (b1) and polysiloxane series latex
Radical polymerization, the step of obtain agglomerate；With the agglomerate for making to obtain and vinyl monomer (b2) glycerol polymerization, ethene is obtained
The step of base system graft copolymer, wherein, vinyl monomer (b1) and (b2) can be the same or different.
Preparation in accordance with the present invention can obtain a kind of graft copolymer of sandwich construction, and the graft copolymer can be with
As anti-impact modifier, it is added in thermoplastic resin, can obtains having excellent low-temperature impact resistance and anti-flammability concurrently
Resin combination.Above-mentioned sandwich construction refers to that polymer beads are made up of with shell kernel, and kernel is possessed respectively with shell
Different performances, the impact to matrix resin are also different.As a rule kernel possesses most of performance of polymer beads itself,
Shell then plays synergistic effect, contributes to dispersion of the particle in matrix resin.
Polysiloxane series latex used in the preparation method of the present invention is preferably with vinyl (active function groups)
Straight chain type polysiloxanes latex.This is because, straight chain type polysiloxane molecule regularity is high, and particle surface is difficult remaining silicon
Alcohol, and the polysiloxane molecule regularity of branched chain type is low, the easy remaining substantial amounts of silanol of particle surface.The silanol of remaining can change
The surface energy of latex particle so that agglomeration is more difficult.And silanol is affected aborning in the factor of the residual quantity of particle surface
More, it is difficult to realize stablizing for production batch, after agglomeration, the particle diameter of product and particle diameter distribution are more difficult to estimate.In addition, by poly-
Vinyl on siloxanes, can import chemical bond between polysiloxanes based polymer and polyvinyl, or grafting
Between monomer component.Contents of ethylene phase from from the viewpoint of obtaining good agglomeration effect, preferably in polysiloxane series latex
For 100 mass % of solid constituent in polysiloxane series latex be 0.01～3 mass %, its lower limit be preferably 0.02 matter
Amount %, more preferably 0.1 mass %, more preferably 0.8 mass %, its higher limit are preferably 2.5 mass %, more preferably
2 mass %, more preferably 1 mass %.
Above-mentioned polysiloxane series latex can by dimethyl silica alkanes monomer, vinylsiloxane class monomer and according to
The closure agent of needs is polymerized and obtains.Crosslinking agent is not used preferably in the manufacture of the polysiloxane series latex of the present invention.This is
Because when using crosslinking agent, easily forming the polysiloxanes of branched chain type, as described above, the polysiloxane molecule rule of branched chain type
Whole degree is low, and the easy remaining substantial amounts of silanol of particle surface, the silanol of remaining can change the surface energy of latex particle so that agglomeration is more
It is difficult.And affect silanol more in the factor of the residual quantity of particle surface aborning, it is difficult to stablizing for production batch is realized,
After agglomeration, the particle diameter of product and particle diameter distribution are more difficult to estimate.Therefore crosslinking agent is not preferably used in the present invention, advantageously form
The polysiloxanes of straight chain type.
As the concrete example of above-mentioned dimethyl silica alkanes monomer, for example, can enumerate hexamethyl cyclotrisiloxane, eight first
Basic ring tetrasiloxane, decamethylcyclopentaandoxane etc., these can be used alone, it is also possible to be mixed with two or more.Its
In, from from the viewpoint of being easily controlled particle diameter distribution, preferably use octamethylcy-clotetrasiloxane.
As the concrete example of above-mentioned vinylsiloxane class monomer, for example, can enumerate γ-(methyl) acryloxy third
Base dimethoxymethylsilane, γ-(methyl) acryloxypropyl diethoxymethylsilane, vinyl methyl dimethoxy
Silane, vinyl methyl diethoxy silane, t etram-ethyltetravinylcyclotetrasiloxane etc., these can be used alone,
Can be mixed with two or more.
As the concrete example of above-mentioned closure agent, for example, can enumerate HMDO, two silicon of tetramethyl divinyl
Oxygen alkane, methoxytrimethylsilane, ethyoxyl trimethicone, dimethylvinylmethoxysiiane, dimethyl ethenyl
Ethoxysilane etc., these can be used alone, it is also possible to be mixed with two or more.
With regard to the manufacture method of polysiloxane series latex, the method that can be listed below.
First, by containing dimethyl silica alkanes monomer, vinylsiloxane class monomer and closure agent as needed
Mix monomer and emulsifying agent, acid catalyst, water etc. mix, obtain monomer emulsions after pre-emulsification.Then, at a certain temperature
Make above-mentioned monomer emulsion polymerization.Finally, with alkaline matter and acid, you can obtain polysiloxane series latex.
The number-average molecular weight (Mn) of above-mentioned polysiloxane series latex is preferably 200,000～600,000, and its lower limit is more preferably 22
Ten thousand, more preferably 240,000, more preferably 260,000, its higher limit more preferably 500,000, more preferably 400,000, further
Preferably 300,000.
In the present invention, in the presence of polysiloxane series latex and vinyl monomer (b1), by polysiloxane series latex
Agglomeration, while make vinyl monomer (b1) and polysiloxane series latex radical polymerization.Before agglomeration, polysiloxane series latex is flat
Particle diameter is preferably 20～80nm.After agglomeration, the average grain diameter of polysiloxane series latex is preferably 100～800nm.Polysiloxanes
Be latex average grain diameter can by change emulsifying agent species and its consumption controlling, it is also possible to by changing vinyl list
The species of body (b1) and its consumption are controlling.Wherein, the impact resistance from the ethene base system graft copolymer for obtaining is (particularly resistance to
Cold temperature impact) from the viewpoint of, before agglomeration, the average grain diameter of polysiloxane series latex is more preferably 25～79nm, more preferably
For 40～78nm, more preferably 60～78nm, the average grain diameter of polysiloxane series latex more preferably 250 after agglomeration～
800nm, more preferably 320～796nm, more preferably 400～780nm.In order that polysiloxane series latex after agglomeration
Average grain diameter be in above range, synthesis agglomerate during, the consumption of emulsifying agent is relative to polysiloxane series latex
Total 100 mass parts of the addition of addition and vinyl monomer (b1) in terms of solid constituent are preferably 0.3～1.2 mass
Part, more preferably 0.4～1.0 mass parts, more preferably 0.5～0.9 mass parts, more preferably 0.5～0.8 mass
Part.In addition, as the emulsifying agent that can carry out agglomeration and radical polymerization simultaneously, can for example enumerate lauryl sodium sulfate,
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, cetyl diphenyl ether sodium disulfonate, sodium dioctylsuccinate, lauryl alcohol polyethers sulfuric acid
Sodium, dodecyl sodium sulfate, neopelex etc..
In the preparation method of the ethene base system graft copolymer of the present invention, by polysiloxane series latex in terms of solid constituent
Addition total of addition, the addition of vinyl monomer (b1) and vinyl monomer (b2) when being set to 100 mass parts,
Addition of the polysiloxane series latex in terms of solid constituent is preferably 20～40 mass parts, vinyl monomer (b1) and vinyl list
Total addition of body (b2) is preferably 60～80 mass parts.From having anti-flammability and impact resistance (particularly low-temperature impact-resistant concurrently
Property) from the viewpoint of, addition of the polysiloxane series latex in terms of solid constituent is more preferably 25～40 mass parts, more preferably
For 30～40 mass parts, more preferably 30～35 mass parts.Vinyl monomer (b1) and vinyl monomer (b2) it is total
Addition is more preferably 60～75 mass parts, more preferably more preferably 60～70 mass parts, 65～70 mass parts.
Addition, the addition of vinyl monomer (b1) and vinyl list by polysiloxane series latex in terms of solid constituent
When the addition of body (b2) total is set to 100 mass parts, the addition of vinyl monomer (b1) is preferably 20～60 mass parts,
More preferably 25～55 mass parts, more preferably 30～50 mass parts, the addition of vinyl monomer (b2) are preferably 20
～40 mass parts, more preferably 22～35 mass parts, more preferably 25～30 mass parts.
In the preparation method of the ethene base system graft copolymer of the present invention, when agglomerate is synthesized, can be by poly- silica
Methane series latex is disposably added in vinyl monomer, it is also possible to polysiloxane series latex is added drop-wise to ethene using fixed speed
In base monomer.For the degree of agglomeration of control system, preferably polysiloxane series latex is disposably added in vinyl monomer,
Carry out agglomeration and radical polymerization simultaneously.The step of with regard to forming agglomerate, by polysiloxanes during agglomeration
Vinyl, can import chemical bond between polysiloxanes based polymer and polyvinyl, form agglomerate.Or with
The polyvinyl for being formed in the course of the polymerization process is bridge, forms agglomerate by polysiloxane series latex agglomeration together.
Vinyl monomer (b1) and (b2) used in the preparation method of the ethene base system graft copolymer of the present invention can
With it is identical can also be different, can for example enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid hydroxyl
Base propyl ester, (methyl) n-butyl acrylate, (methyl) acrylic acid, (methyl) Isooctyl acrylate monomer, (methyl) acrylonitrile, N- hydroxyl first
Base acrylamide, styrene and (methyl) isobornyl acrylate etc..These vinyl monomers can be used alone, and also may be used
To be mixed with two or more.
In the step of forming ethene base system graft copolymer, when making agglomerate and vinyl monomer (b2) graft copolymerization,
From conventional emulsion polymerization way, and preferably added using starvation method.For the ethene base system graft copolymerization obtained by controlling
The molecular weight and percent grafting of the butanone soluble ingredient of thing, can suitably rise high-temperature and addition molecular chain transfer agent.From raising
Ethene base system graft copolymer adds appropriate dividing from the viewpoint of the dispersiveness in resin, preferably as anti-impact modifier
Subchain transfer agent.
In the step of forming agglomerate and form graft copolymer, inorganic peroxide, organic peroxy can be adopted
The polymerization initiator of more than a kind in thing and azo series initiators, makes polysiloxane series latex or agglomerate and vinyl list
Body is polymerized and obtains compounded latex.
As inorganic peroxide, hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate etc. can be enumerated.These inorganic peroxygens
Thing can be used alone, it is also possible to be mixed with two or more.
As organic peroxide, dibenzoyl peroxide, cumyl peroxide, hydrogen peroxide isopropyl can be enumerated
Benzene, TBHP, the new heptanoic acid tert-butyl ester of peroxidating, peroxysuccinic acid, peroxide -2-ethyl hexanoic acid tert-butyl, mistake
Oxidation neopentanoic acid tert-butyl ester etc..These organic peroxides can be used alone, it is also possible to be mixed with two or more.
As azo series initiators, 2 can be enumerated, 2 '-azodiisobutyronitrile, 2,2 '-ABVN, 4,4 '-even
Double [N- (2- the carboxymethyls) -2- methyl-prop amidines] hydrates of nitrogen double (4- cyanopentanoic acids), 2,2 '-azo, 2,2 '-azo it is double (N, N ' -
Dimethyleneisobutylamidine) dihydrochloride and double [2- (2- imidazoline -2- bases) propane] dihydrochlorides of 2,2 '-azo etc..These idols
Nitrogen series initiators can be used alone, it is also possible to be mixed with two or more.
In addition, with regard to ethene base system graft copolymer obtained from the preparation method by the present invention, its butanone not melt into
Divide and be preferably more than 80 mass %, more than more preferably 90 mass %, more preferably 95 mass %, more preferably 97 matter
Amount more than %.When above-mentioned butanone insoluble component is less than 80 mass %, the impact resistance of composition can be affected.Resulting ethene
The number-average molecular weight (Mn) of the butanone soluble ingredient of base system graft copolymer is preferably 10000～140000, and its lower limit is more excellent
Elect 40000, more preferably 50000, more preferably 60000 as, its higher limit is more preferably 120000, more preferably
110000, more preferably 100000.When the number-average molecular weight (Mn) of above-mentioned butanone soluble ingredient is higher than 10000, should
Ethene base system graft copolymer be added in thermoplastic resin obtained from resin combination low-temperature impact resistance it is good, when upper
When the number-average molecular weight (Mn) of butanone soluble ingredient is stated less than 140000, the ethene base system graft copolymer is added to into thermoplasticity
The transparency of resin combination obtained from resin is good.The weight of the butanone soluble ingredient of other ethene base system graft copolymer
The ratio (Mw/Mn) of average molecular weight (Mw) and number-average molecular weight (Mn) is preferably 2.0～3.0.Mw/Mn more preferably 2.5～3.0.
The resin combination of the present invention contains ethene base system graft copolymer and resin (particularly thermoplastic resin).Its
In, during ethene base system graft copolymer generally adds resin (particularly thermoplastic resin) in the form of powder.Ethene base system connects
The powder of graft copolymer is condensed by the ethene base system graft copolymer to being obtained by above-mentioned preparation method, dry, broken
Etc. a series of aftertreatment technologys, the powder of ethene base system graft copolymer is finally given.
As thermoplastic resin, can enumerate polystyrene (PS), (methyl) acrylate styrene copolymer (MS),
Styrene acrylonitrile copolymer (SAN), acrylonitrile butadient styrene (ABS), acrylate benzene second
Alkene acrylonitrile copolymer (ASA), acrylonitrile EP rubbers styrol copolymer (AES), polymethyl methacrylate
(PMMA), Merlon (PC), PET (PET), polybutylene terephthalate (PBT) (PBT) etc..These
Thermoplastic resin can be used alone, it is also possible to be mixed with two or more.
With regard to the content of the ethene base system graft copolymer in resin combination, relative to 100 mass parts of thermoplastic resin
Preferably 1～35 mass parts, more preferably 2～20 mass parts, more preferably 3～10 mass parts.Wherein, in ethene base system
When the content of graft copolymer is more than 1 mass parts, composition transparency height, impact resistance and the anti-flammability for obtaining is all good,
When below 35 mass parts, without compromising on the original characteristic of thermoplastic resin, and resistance to impact, the transparency and anti-flammability reach
Optimum value.
Preferably also containing antioxidant, lubricant, anti-dripping agent, filler and the pigment being usually used in resin combination
In more than a kind.As antioxidant, for example, can enumerate phosphorous antioxidant, phenol antioxidant etc..As lubricant,
Stearic acid, tristerin, paraffin, polyvinyl paraffin wax etc. can for example be enumerated.As anti-dripping agent, for example, can enumerate
PTFE etc..As filler, for example, can enumerate calcium carbonate, magnesium hydroxide, titanium dioxide etc..As pigment, for example, can enumerate
Iron oxide red, iron oxide yellow, zinc-iron Huang etc..
In the present invention, the measure of each physical property is carried out by the following method.
(1) low temperature impact strength
Impact strength adopts GB/T 1843-2008《The measure of cantilever beam impact strength》Standard tested, and with thousand
Per square metre of (kJ/m of Jiao2) represent.Wherein, it is with regard to low temperature impact strength, batten is little in -30 DEG C and -40 DEG C of constant temperature placements 48
Shi Hou, measures Izod notched impact strength.
(2) butanone insoluble component
Using apparatus,Soxhlet's, 1g ethene base system graft copolymer powders are flowed back 8 hours in 100ml butanone, filtered
Separate butanone insoluble component.After the butanone insoluble component isolated is dried 24 hours at 80 DEG C with vacuum drier, determine
Quality.Butanone insoluble component can be wherein calculated as follows.
Butanone insoluble component (%)=100 × (quality of dried butanone insoluble component)/(powder before surname extraction
Quality).
(3) percent grafting
The butanone insoluble component that said method is obtained, calculates percent grafting according to equation below.
Percent grafting=(vinyl monomer (b2) amount in grafting)/(vinyl monomer (b2) total amount before grafting) ×
100%
(4) number-average molecular weight/weight average molecular weight
With regard to the measure of the number-average molecular weight/weight average molecular weight of the butanone soluble ingredient of ethene base system graft copolymer, receive
The butanone soluble ingredient of collection ethene base system graft copolymer, is dried 24 hours at 80 DEG C with vacuum drier.Oozed using gel
Chromatography (GPC), determines the molecular weight (number-average molecular weight/weight average molecular weight) of the DDGS for obtaining thoroughly.When carrying out GPC measure,
Eluent is THF, and temperature is 23 ± 2 DEG C.
It is same as the above-mentioned method with regard to the measure of the number-average molecular weight of polysiloxane series latex, i.e. by polysiloxane series
Latex vacuum drier is dried 24 hours at 80 DEG C.The dried object obtained using gel permeation chromatography (GPC), measure
Molecular weight (number-average molecular weight/weight average molecular weight).When carrying out GPC measure, eluent is THF, and temperature is 23 ± 2 DEG C.
(5) anti-flammability
Sheet-like formed body is cut into into thickness 3mm × width 12.7mm × length 127mm, 5 equivalent specifications samples of parallel making
Bar, places them in the environment of 23 DEG C of temperature, humidity 50% after 24 hours, carries out UL94 tests.Make to take off in calculating batten
What fat cotton caught fire has the radical of flame dropping generation.Radical is fewer, and anti-flammability is more excellent.
(6) heat-resistant aging
By test film (length 80.0mm, width 10.0mm, thickness 4mm), in the baking oven of 120 DEG C of temperature, heat treatment 12 is little
When.Test film is taken out from baking oven, is placed more than 24 hours in the environment of 23 DEG C of temperature, relative humidity 50%, then in temperature
23 DEG C, impact strength is determined, as the index of heat-resistant aging.
(7) heat resistance
Using the assay method described in GB GB/T1634-2001, heating rate is set as 120 DEG C/h, deflection is
0.21mm.It is zero to adjust deflection measurement apparatus every time before test and make deflection.
(8) average grain diameter
Using distilled water as mobile phase, latex is added dropwise over into Britain LS-230Coulter laser light scattering test ponds,
Determine the average grain diameter of polymer beads in latex.
Embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Unless stated otherwise, material involved in embodiment, method are material commonly used in the art and method.In addition, with regard to this
" part ", " % " in specification, unless stated otherwise, represents " mass parts ", " quality % " respectively.
1. the Production Example of polysiloxane series latex is as follows.
Embodiment 1
(1) add 61 parts in the four-hole boiling flask for possessing electric mixer, constant pressure funnel, thermometer and condenser pipe to go
The mixture of ionized water and 0.6 part of DBSA, turn on agitator, and temperature is risen to into 70 DEG C, make temperature keep permanent
It is fixed.Then by 1.6 parts of hexamethyl cyclotrisiloxanes, 28 parts of octamethylcy-clotetrasiloxanes and 3 parts of γ-(methyl) acryloxies third
Conduct after base dimethoxymethylsilane is well mixed is added dropwise component, in being added dropwise over constant pressure funnel, and is dripped with 2 hours
It is complete, 2 hours are incubated after completion of dropping.
(2) by 124 parts of deionized waters, 1 part of neopelex, 3.4 parts of hexamethyl cyclotrisiloxanes, 57 part of eight first
Basic ring tetrasiloxane, 5 parts of γ-(methyl) acryloxypropyl diethoxymethylsilanes and 2 parts of HMDOs are mixed
After conjunction, homogenous disperse in high shear dispersion homogenizer is placed in.Then it is added drop-wise in above-mentioned system with constant pressure funnel, it is little with 4
When drip off after, temperature is risen to into 80 DEG C, be incubated 10 hours.
(3) after the completion of being polymerized, treat that emulsion is cooled to room temperature, it is 7-8 pH value to be neutralized to ammoniacal liquor, obtains final product polysiloxanes latex
(G1)。
Embodiment 2
(1) add 61 parts in the four-hole boiling flask for possessing electric mixer, constant pressure funnel, thermometer and condenser pipe to go
The mixture of ionized water and 0.75 part of DBSA, turn on agitator, and temperature is risen to into 70 DEG C, make temperature keep permanent
It is fixed.Then by 1.8 parts of decamethylcyclopentaandoxanes, 30.9 parts of octamethylcy-clotetrasiloxanes and 0.096 part of γ-(methyl) acryloyl
Conduct after epoxide propyl group diethoxymethylsilane is well mixed is added dropwise component, is added dropwise over four-hole boiling flask with constant pressure funnel
In, and dripped off with 2 hours, 2 hours are incubated after completion of dropping.
(2) by 124 parts of deionized waters, 1.25 parts of neopelexes, 3.6 parts of hexamethyl cyclotrisiloxanes, 61.7
After part octamethylcy-clotetrasiloxane, 1 part of tetramethyl divinyl disiloxane and 1 part of methoxytrimethylsilane mixing, it is placed in
Homogenous disperse in high shear dispersion homogenizer.Then it is added drop-wise in above-mentioned system with constant pressure funnel, after being dripped off with 4 hours,
Temperature is risen to into 80 DEG C, 10 hours are incubated.
(3) after the completion of being polymerized, treat that emulsion is cooled to room temperature, it is 7-8 pH value to be neutralized to ammoniacal liquor, obtains final product polysiloxanes latex
(G2)。
Embodiment 3
(1) add 61 parts in the four-hole boiling flask for possessing electric mixer, constant pressure funnel, thermometer and condenser pipe to go
The mixture of ionized water and 0.6 part of DBSA, turn on agitator, and temperature is risen to into 70 DEG C, make temperature keep permanent
It is fixed.Then by 4.8 parts of t etram-ethyltetravinylcyclotetrasiloxanes, 28.1 parts of octamethylcy-clotetrasiloxanes and 1 part of ethyoxyl front three
Conduct after radical siloxane is well mixed is added dropwise component, is added dropwise in four-hole boiling flask with constant pressure funnel, and is dripped with 2 hours
It is complete, 2 hours are incubated after completion of dropping.
(2) by 124 parts of deionized waters, 1 part of neopelex, 8.9 parts of vinyl methyl diethoxy silanes,
After 56.2 parts of octamethylcy-clotetrasiloxanes and 1 part of Vinyldimethylethoxysilane mixing, high shear dispersion homogenizer is placed in
Middle homogenous disperse.Then it is added drop-wise in above-mentioned system with constant pressure funnel, after dripping off with 4 hours, temperature is risen to into 80 DEG C, is protected
Temperature 10 hours.
(3) after the completion of being polymerized, treat that emulsion is cooled to room temperature, it is 7-8 pH value to be neutralized to ammoniacal liquor, obtains final product polysiloxanes latex
(G3)。
Solid component content in the polysiloxane series latex of embodiment 1-3 is for about 35%.
Contents of ethylene in polysiloxane series latex is (relative to 100 matter of solid constituent in polysiloxane series latex
Amount %) and the molecular weight of polysiloxane series latex it is as shown in table 1.
Table 1
2. the Production Example of ethene base system graft copolymer is as follows.
Embodiment 4
(1) by 4 parts of Isooctyl acrylate monomers, 16 parts of methyl acrylates, 0.4 part of dodecyl sodium sulfate and 30 parts of deionized waters
High shear dispersion is carried out after mixing, is added to the four-hole boiling flask equipped with electric mixer, nitrogen ingress pipe, thermometer and condenser pipe
In.Start stirring, be passed through nitrogen, be warmed up to 70 DEG C.When reaction system rises to 60 DEG C, 0.06 part of ammonium persulfate of addition, and while
114.2 parts of the polysiloxanes latex (G1) (being scaled 40 parts with solid constituent) that input embodiment 1 is obtained.And keep 70 DEG C of reactions
4 hours, obtain polymerized emulsion.
(2) 0.12 part of sodium formaldehyde sulfoxylate, 0.0014 part of ferrous sulfate, 0.0014 part of ethylenediamine tetra-acetic acid are added to into above-mentioned (1)
Polymerized emulsion in.And by 15 parts of methyl methacrylates, 3 parts of isobornyl methacrylates, 2 parts of acrylonitrile, 0.006 part of uncle
DDM dodecyl mercaptan, 0.06 part of dicumyl peroxide, 0.4 part of dodecyl sodium sulfate, 0.2 part of OPEO (OP-
10) He 19.6 parts of deionized water mixing shearing dispersions, are then also added drop-wise in the polymerized emulsion of above-mentioned (1), were dripped off with 8 hours.
After dripping off, reaction temperature is risen to into 75 DEG C, be incubated 4 hours.
(3) 1wt% calcium chloride solutions are added, is warming up to 70 DEG C of breakdowns of emulsion, washing centrifugation is then placed in vacuum drying chamber.
80 DEG C of dryings 24 hours, obtain white powder.And extracted to remove unreacted monomer and homopolymers with Soxhlet extractor, you can
Ethene base system graft copolymer after must purifying.
Embodiment 5
(1) 30 parts of hydroxypropyl acrylates, 30 parts of ethyl acrylates, 0.4 part of neopelex and 90 parts are gone
High shear dispersion is carried out after ionized water mixing, equipped with electric mixer, nitrogen ingress pipe, thermometer and condenser pipe four are added to
In mouth flask.Start stirring, be passed through nitrogen, be warmed up to 70 DEG C.When reaction system rises to 60 DEG C, 0.18 part of ammonium persulfate is added,
And while put into 57.1 parts of the polysiloxanes latex (G2) (20 parts being scaled with solid constituent) that embodiment 2 is obtained.And keep 70
DEG C reaction 4 hours, obtain polymerized emulsion.
(2) 0.16 part of L-AA, 0.001 part of ferrous sulfate, 0.001 part of ethylenediamine tetra-acetic acid are added to above-mentioned
(1) in polymerized emulsion.And by 15 parts of methyl methacrylates, 5 parts of N hydroxymethyl acrylamides, 0.004 part of 12 carbon sulphur of uncle
Alcohol, 0.08 part of TBHP, 0.4 part of dodecyl sodium sulfate and 19.6 parts of deionized waters mix and shear dispersion, so
Also it is added drop-wise in the polymerized emulsion of above-mentioned (1) afterwards, was dripped off with 8 hours.After dripping off, reaction temperature is risen to into 75 DEG C, insulation 4 is little
When.
(3) 1.0wt%CaCl solution is added, is warming up to 70 DEG C of breakdowns of emulsion, washing centrifugation is then placed in vacuum drying chamber.
80 DEG C of dryings 24 hours, obtain white powder.And extracted to remove unreacted monomer and homopolymers with Soxhlet extractor, you can
Ethene base system graft copolymer after must purifying.
Embodiment 6
(1) by 15 parts of EMAs, 15 parts of butyl acrylates, 0.3 part of dodecyl sodium sulfate and 45 parts go from
High shear dispersion is carried out after sub- water mixing, equipped with electric mixer, nitrogen ingress pipe, thermometer and condenser pipe four mouthfuls are added to
In flask.Start stirring, be passed through nitrogen, be warmed up to 65 DEG C.When reaction system rises to 55 DEG C, 0.09 part 2 is added, 2 '-azo is double
(N, N '-dimethyleneisobutylamidine) dihydrochloride, and while put into 85.7 parts of the polysiloxanes latex (G3) that embodiment 3 is obtained
(being scaled 30 parts with solid constituent).And kept for 60 DEG C react 4 hours, obtain polymerized emulsion.
(2) 0.28 part of sodium formaldehyde sulfoxylate, 0.002 part of ferrous sulfate, 0.002 part of ethylenediamine tetra-acetic acid are added to into above-mentioned (1)
In polymerized emulsion.And by 28 parts of methacrylic acids, 10 parts of hydroxy propyl methacrylates, 2 parts of butyl methacrylates, 0.008
Part tert-dodecyl mercaptan, 0.14 part of dicumyl peroxide, 0.8 part of dodecyl sodium sulfate and 39.2 parts of deionized waters mix and cut
Cutting dissipates, and is then also added drop-wise in the polymerized emulsion of above-mentioned (1), was dripped off with 8 hours.After dripping off, reaction temperature is risen to into 75 DEG C,
Insulation 4 hours.
(3) 1.0wt% calcium chloride solutions, breakdown of emulsion under room temperature, washing centrifugation is added to be then placed in vacuum drying chamber.80
DEG C drying 24 hours, obtains white powder.And extracted to remove unreacted monomer and homopolymers with Soxhlet extractor, you can
Ethene base system graft copolymer after purification.
Embodiment 7
(1) by 8.3 parts of n-butyl acrylates, 16.7 parts of butyl methacrylates, 0.5 part of dodecyl sodium sulfate and 37.5
High shear dispersion is carried out after part deionized water mixing, is added to equipped with electric mixer, nitrogen ingress pipe, thermometer and condenser pipe
Four-hole boiling flask in.Start stirring, be passed through nitrogen, be warmed up to 55 DEG C.When reaction system rises to 45 DEG C, 0.075 part 2 is added, 2 '-
Double [2- (2- imidazoline -2- bases) propane] dihydrochlorides of azo, and while put into the polysiloxanes latex (G1) that embodiment 1 is obtained
100 parts (being scaled 35 parts with solid constituent).And kept for 50 DEG C react 4 hours, obtain polymerized emulsion.
(2) 0.26 part of sodium formaldehyde sulfoxylate, 0.002 part of ferrous sulfate, 0.002 part of ethylenediamine tetra-acetic acid are added to into above-mentioned (1)
In polymerized emulsion.And by 20 parts of methyl methacrylates, 15 parts of acrylic acid, 5 parts of acrylonitrile, 0.008 part of tert-dodecyl mercaptan,
0.13 part of dicumyl peroxide, 0.8 part of dodecyl sodium sulfate and 39.2 parts of deionized waters mix and shear dispersion, then also drip
It is added in the emulsion of above-mentioned (1), was dripped off with 8 hours.After dripping off, reaction temperature is risen to into 75 DEG C, be incubated 4 hours.
(3) 1.0wt% calcium chloride solutions are added, is warming up to 70 DEG C of breakdowns of emulsion, washing centrifugation is then placed in vacuum drying chamber
In.80 DEG C of dryings 24 hours, obtain white powder.And extracted with Soxhlet extractor to remove unreacted monomer and homopolymers,
Ethene base system graft copolymer after must can purifying.
Embodiment 8
(1) by 17.5 parts of ethyl acrylates, 17.5 parts of EHMAs, 0.7 part of neopelex and
High shear dispersion is carried out after the mixing of 52.5 parts of deionized waters, is added to equipped with electric mixer, nitrogen ingress pipe, thermometer and cold
In the four-hole boiling flask of solidifying pipe.Start stirring, be passed through nitrogen, be warmed up to 65 DEG C.When reaction system rises to 55 DEG C, 0.105 part is added
2, double (N, N '-dimethyleneisobutylamidine) dihydrochloride of 2 '-azo, and while put into the poly- silicon that 114.2 parts of embodiments 2 are obtained
Oxygen alkane latex (G2) (is scaled 40 parts with solid constituent).And kept for 60 DEG C react 4 hours, obtain polymerized emulsion.
(2) 0.25 part of L-AA, 0.004 part of ferrous sulfate, 0.004 part of ethylenediamine tetra-acetic acid are added to above-mentioned
(1) in polymerized emulsion.And by 10 parts of EMAs, 15 parts of isobornyl methacrylates, 0.005 part of 12 carbon of uncle
Mercaptan, 0.125 part of TBHP, 0.5 part of dodecyl sodium sulfate, 0.25 part of OPEO (OP-10)
High speed shear dispersion is carried out with after the mixing of 34 parts of deionized waters, is then also added drop-wise in above-mentioned (1) in emulsion, was dripped off with 8 hours.
After dripping off, temperature is risen to into 75 DEG C, be incubated 4 hours.
(3) 1.0wt% calcium chloride solutions, breakdown of emulsion under room temperature, washing centrifugation is added to be then placed in vacuum drying chamber.80
DEG C drying 24 hours, obtains white powder.And extracted to remove unreacted monomer and homopolymers with Soxhlet extractor, you can
Ethene base system graft copolymer after purification.
Comparative example 1
Except the addition of vinyl monomer (b1) ethyl acrylate to be changed into the use of 5 parts and EHMA
Quantitative change is 5 parts, also, the addition of vinyl monomer (b2) EMA and isobornyl methacrylate is changed into
23 parts and 27 parts in addition, and ethene base system graft copolymer is obtained in method similarly to Example 8.
Comparative example 2
Except the addition of vinyl monomer (b1) ethyl acrylate to be changed into the use of 35 parts and hydroxypropyl acrylate
Quantitative change is 35 parts, also, the addition of vinyl monomer (b2) methyl methacrylate and N hydroxymethyl acrylamide is changed into
7.5 parts and 2.5 parts in addition, and ethene base system graft copolymer is obtained in method similarly to Example 5.
Comparative example 3
Except synthesize agglomerate when the consumption of emulsifying agent neopelex is changed to into 1.05 especially, with reality
Apply the same method of example 8 and obtain ethene base system graft copolymer.
Comparative example 4
Except synthesize agglomerate when the consumption of emulsifying agent dodecyl sodium sulfate is changed to into 0.15 especially, with enforcement
The same method of example 6 obtains graft copolymer.
Comparative example 5：In the embodiment 1 of Chinese patent application CN103391952 (A), the polymer of gained (is not carried out attached
It is poly-).
Comparative example 6：The product of model S2100 produced by Mitsubishi Li Yang Co., Ltd..
Polysiloxane series latex, vinyl monomer (b1) and vinyl list used in embodiment 4-8 and comparative example 1-5
The ratio and polymer property of body (b2) three is as shown in table 2.
3. the preparation and evaluation of resin combination
According to the ratio that table 3 is recorded, by the powder of ethene base system graft copolymer and PC resin (Mitsubishi Engineering-Plastics (strain)
Production, trade name：S-2000F) mix, using double screw extruder (Jie Ente electromechanics Co., Ltd SHJ-36) in mold temperature
Under conditions of for 280 DEG C, melting mixing is carried out.Then add phosphorous antioxidant (trade name：ADEAKSTAB PEP36, strain formula
Commercial firm ADEKA is produced) 0.3 part, phenol antioxidant (trade name：Irganox245, the production of German BASF group) 0.3 part and
(Japan AGC company produces PTFE, trade name：FULLON CD123E) 0.05 part, continue stirring mixing, obtain resin combination
Thing.Then, it is made into graininess.
After the particle for obtaining is dried 12 hours at 80 DEG C, with injection moulding machine (Yin Zhou Shuansheng plastics machineries factory
SSF500- III) the injection mo(u)ldings under conditions of 280 DEG C.As requested, using multi-cavity metal die, respectively be obtained impact test,
Combustion test and the test film of heat-resistant aging test.Using particle and test film, impact strength, anti-flammability and heat-resisting is evaluated
The performances such as aging, heat resistance, as a result as shown in table 3.
From table 2,3, in comparative example 1, add the amount of vinyl monomer (b1) very few, compared with Example 8, percent grafting
Reduce, the low-temperature impact resistance of resulting resin combination, anti-flammability and heat-resistant aging decline.
In addition, in comparative example 2, add the amount of vinyl monomer (b1) excessive, and compared with Example 5, resulting resin group
The heat distortion temperature of compound is reduced, and low-temperature impact resistance, anti-flammability and heat-resistant aging decline.
As the average grain diameter of polysiloxane series latex after agglomeration is too small in comparative example 3, particle diameter is in 100nm particles below
Number is more.Compared with Example 8, the performance such as the low-temperature impact resistance of resulting resin combination, heat-resistant aging is not
Good effect can be reached.
As the average grain diameter of polysiloxane series latex after agglomeration is excessive in comparative example 4, particle of the particle diameter in more than 800nm
Number is more.The performances such as the low-temperature impact resistance of resulting resin combination, anti-flammability and heat-resistant aging are not strictly according to the facts
Apply example 6.
The resin combination of the ethene base system graft copolymer powder obtained in adding embodiment 4-8, with excellent
Low-temperature impact resistance, anti-flammability and heat-resistant aging.And connect due to present invention employs specific method synthesizing ethylene base system
Graft copolymer so that after being added into thermoplastic resin, the low-temperature impact resistance of resulting resin combination, anti-flammability and resistance to
It is hot be all better than add comparative example 5 and comparative example 6 in the resin combination of graft copolymer that manufactures.
Above-described embodiment is the present invention preferably embodiment, but the present invention is not restricted to these embodiments, as long as
Spirit Essence and principle without departing substantially from the present invention, the change made to above-described embodiment, modification, replacement, combination, simplification are accordingly to be regarded as
Equivalent method of replacing, is included within protection scope of the present invention.
Industrial applicability
Ethene base system graft copolymer according to the present invention can be mixed with the thermoplastic resin such as PC, prepare low-temperature impact-resistant
The resin combination of property and excellent in flame retardance.The resin combination of the present invention can be widely applied to electronic apparatus and industrial machinery zero
Part.
Claims (10)
1. a kind of preparation method of ethene base system graft copolymer, it is characterised in that include：
In the presence of polysiloxane series latex and vinyl monomer b1, by polysiloxane series latex agglomeration, while making vinyl
Monomer b1 and polysiloxane series latex radical polymerization, the step of obtain agglomerate；With
The agglomerate that obtains and vinyl monomer b2 glycerol polymerizations is made, the step of obtain ethene base system graft copolymer,
Wherein, vinyl monomer b1 and b2 can be the same or different.
2. preparation method as claimed in claim 1, it is characterised in that：
The polysiloxane series latex is the latex of the straight chain type polysiloxanes with vinyl, in the polysiloxane series latex
Contents of ethylene relative to 100 mass % of solid constituent in the polysiloxane series latex be 0.01～3 mass %.
3. preparation method as claimed in claim 1 or 2, it is characterised in that：
The polysiloxane series latex is by making dimethyl silica alkanes monomer, vinylsiloxane class monomer and as needed
Closure agent polymerization is obtained, and does not use crosslinking agent in the manufacture of the polysiloxane series latex, the polysiloxane series latex
Number-average molecular weight Mn is 200,000～600,000.
4. preparation method as claimed in claim 1 or 2, it is characterised in that：
Before agglomeration, the average grain diameter of polysiloxane series latex is 20～80nm, and after agglomeration, the average grain diameter of polysiloxane series latex is
100～800nm.
5. preparation method as claimed in claim 1 or 2, it is characterised in that：
Addition, the addition of the vinyl monomer b1 and the second by the polysiloxane series latex in terms of solid constituent
When the addition of alkenyl monomer b2 total is set to 100 mass parts, addition of the polysiloxane series latex in terms of solid constituent
Measure for 20～40 mass parts, the vinyl monomer b1 and the vinyl monomer b2 total addition be 60～80 mass
Part.
6. preparation method as claimed in claim 1 or 2, it is characterised in that：
Addition, the addition of the vinyl monomer b1 and the second by the polysiloxane series latex in terms of solid constituent
When the addition of alkenyl monomer b2 total is set to 100 mass parts, the addition of the vinyl monomer b1 is 20～60 mass
Part, the addition of the vinyl monomer b2 is 20～40 mass parts.
7. preparation method as claimed in claim 1 or 2, it is characterised in that：
The vinyl monomer b1 and vinyl monomer b2 selected from (methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) hydroxypropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid, (methyl) Isooctyl acrylate monomer, (first
Base) more than a kind in acrylonitrile, N hydroxymethyl acrylamide, styrene and (methyl) isobornyl acrylate.
8. ethene base system graft copolymer obtained from a kind of preparation method by any one of claim 1～7, its
It is characterised by：
The butanone insoluble component of the ethene base system graft copolymer is more than 80 mass %.
9. ethene base system graft copolymer as claimed in claim 8, it is characterised in that：
Number-average molecular weight Mn of the butanone soluble ingredient of the ethene base system graft copolymer is 10000～140000, is divided equally again
The ratio of son amount Mw and number-average molecular weight Mn is calculated as 2.0～3.0 with Mw/Mn.
10. a kind of resin combination, it is characterised in that：
Containing ethene base system graft copolymer and thermoplastic resin described in claim 8 or 9.
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| CN201610789392.3A CN106519144B (en) | 2016-08-31 | 2016-08-31 | The preparation method of ethylene base system graft copolymer and resin combination and ethylene base system graft copolymer containing it |
| PCT/CN2016/106196 WO2018040297A1 (en) | 2016-08-31 | 2016-11-17 | Vinyl graft copolymer and resin composition comprising same, and method for preparing said vinyl graft copolymer |
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| CN201610789392.3A CN106519144B (en) | 2016-08-31 | 2016-08-31 | The preparation method of ethylene base system graft copolymer and resin combination and ethylene base system graft copolymer containing it |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107151296A (en) * | 2017-04-18 | 2017-09-12 | 华南理工大学 | The preparation method of big particle diameter core shell structure silicone acrylates/styrol copolymer |
| CN107602861A (en) * | 2017-08-28 | 2018-01-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of waterborne flame retardant fluorine containing silicone oil and preparation method thereof |
| CN110591098A (en) * | 2019-10-09 | 2019-12-20 | 浙江新安化工集团股份有限公司 | Methyl phenyl vinyl silicone oil and preparation method and application thereof |
| WO2020175300A1 (en) * | 2019-02-28 | 2020-09-03 | 日信化学工業株式会社 | Emulsion composition of (meth)acrylic silicone resin, fabric treatment agent containing said composition, and fabric treated with said fabric treatment agent |
| CN116411476A (en) * | 2021-12-30 | 2023-07-11 | 广州熵能创新材料股份有限公司 | Anti-sticking barrier composition for paper and plastic, preparation method thereof and pulp molded product prepared from anti-sticking barrier composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103391952A (en) * | 2010-12-28 | 2013-11-13 | 三菱丽阳株式会社 | Graft copolymer and production method therefor, resin composition, and molded article |
| JP2014034656A (en) * | 2012-08-09 | 2014-02-24 | Mitsubishi Rayon Co Ltd | Polyorganosiloxane-containing graft copolymer, resin composition including the same, and molding |
| CN105636997A (en) * | 2013-08-13 | 2016-06-01 | 三菱丽阳株式会社 | Polyorganosiloxane-containing graft copolymer, resin composition, molded article, sliding-properties improvement agent, and sliding member |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4112421B2 (en) * | 2003-05-01 | 2008-07-02 | 三菱レイヨン株式会社 | Graft copolymer and thermoplastic resin composition using the same |
| JP2004346271A (en) * | 2003-05-26 | 2004-12-09 | Mitsubishi Rayon Co Ltd | Silicone/acrylic compound rubber type graft copolymer and thermoplastic resin composition |
| CN107286300B (en) * | 2012-10-31 | 2021-09-28 | 三菱化学株式会社 | Polyorganosiloxane-containing graft copolymer, resin composition, and molded article |
-
2016
- 2016-08-31 CN CN201610789392.3A patent/CN106519144B/en active Active
- 2016-11-17 WO PCT/CN2016/106196 patent/WO2018040297A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103391952A (en) * | 2010-12-28 | 2013-11-13 | 三菱丽阳株式会社 | Graft copolymer and production method therefor, resin composition, and molded article |
| JP2014034656A (en) * | 2012-08-09 | 2014-02-24 | Mitsubishi Rayon Co Ltd | Polyorganosiloxane-containing graft copolymer, resin composition including the same, and molding |
| CN105636997A (en) * | 2013-08-13 | 2016-06-01 | 三菱丽阳株式会社 | Polyorganosiloxane-containing graft copolymer, resin composition, molded article, sliding-properties improvement agent, and sliding member |
Non-Patent Citations (1)
| Title |
|---|
| "《塑料橡胶加工助剂》" * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107151296A (en) * | 2017-04-18 | 2017-09-12 | 华南理工大学 | The preparation method of big particle diameter core shell structure silicone acrylates/styrol copolymer |
| WO2018192222A1 (en) * | 2017-04-18 | 2018-10-25 | 华南理工大学 | Preparation method for polysiloxane-acrylate/styrene copolymer with large particle size and core-shell structure |
| CN107602861A (en) * | 2017-08-28 | 2018-01-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of waterborne flame retardant fluorine containing silicone oil and preparation method thereof |
| CN107602861B (en) * | 2017-08-28 | 2021-01-12 | 哈尔滨工业大学无锡新材料研究院 | Water-based flame-retardant fluorine-containing silicone oil and preparation method thereof |
| WO2020175300A1 (en) * | 2019-02-28 | 2020-09-03 | 日信化学工業株式会社 | Emulsion composition of (meth)acrylic silicone resin, fabric treatment agent containing said composition, and fabric treated with said fabric treatment agent |
| CN110591098A (en) * | 2019-10-09 | 2019-12-20 | 浙江新安化工集团股份有限公司 | Methyl phenyl vinyl silicone oil and preparation method and application thereof |
| CN116411476A (en) * | 2021-12-30 | 2023-07-11 | 广州熵能创新材料股份有限公司 | Anti-sticking barrier composition for paper and plastic, preparation method thereof and pulp molded product prepared from anti-sticking barrier composition |
| CN116411476B (en) * | 2021-12-30 | 2024-02-23 | 广州熵能创新材料股份有限公司 | Anti-sticking barrier composition for paper and plastic, preparation method thereof and pulp molded product prepared from anti-sticking barrier composition |
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| CN106519144B (en) | 2019-06-04 |
| WO2018040297A1 (en) | 2018-03-08 |
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