CN104558428B - Preparation method of high-toughened chloroethylene grafted copolymer - Google Patents
Preparation method of high-toughened chloroethylene grafted copolymer Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-toughened chloroethylene grafted copolymer, and belongs to the field of high polymer materials. The preparation method is characterized in that the graft copolymerization process is divided into two stages for preparing the chloroethylene grafted copolymer, wherein the first stage is to prepare acrylate rubber latex which adopts a core-shell structure and is rich in unsaturated double bond active grafting sites on the surface; the second stage is to carry out graft copolymerization to 1-10% of the acrylate rubber latex and 90-99% of chloroethylene in mass fraction; the acrylate monomer is copolymerized with the crosslinking monomers containing two or more non-conjugated double bonds to prepare the crosslinked polymer latex as a core, and then the crosslinking monomers are polymerized on the surface of the core to form a shell, so as to prepare the acrylate rubber latex, the average grain diameter of which is 0.080-0.500 microns. The copolymer resin prepared by the preparation method disclosed by the invention is excellent in shock strength and processability; the extra impact modifier is not required to be used.
Description
Technical field
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer, belongs to technical field of polymer materials, specifically relates to
And a kind of chloride graft polymer toughness reinforcing by acrylate polymer.
Background technology
Corvic manufactured goods are cheap, and have good processing characteristics, mechanical performance and chemically
Stability, is widely used in daily life and field of industrial production.Owing to the fragility of Corvic own is relatively big, need to carry
Its intensity high and toughness.
For improving intensity and the toughness of resin, all multi-methods are suggested, and mainly have physical mixing processes and chemistry
Method of modifying.Physical modification method is included in the Corvic course of processing and adds shock resistance in the middle of Corvic
Modifying agent such as MBS (MBS terpolymer) resin, shock resistance ACR(esters of acrylic acid)
Resin, CPE (chlorinated polyethylene) resin and other reinforcing agent compositions etc., these compositions that Corvic is strengthened
Need to be distributed in matrix resin in the course of processing, thus be subject to processing the many factors such as formula, temperature conditions, mixing condition
Impact, mechanical stability can not well be ensured, and manufacture these reinforcing agents time employ promotion dispersion
Composition with improving with matrix resin cohesive force, have impact on impact modification effect, adds manufacturing cost.
For improving the shock resistance of Corvic product, improve mechanical performance index and constant product quality,
The chemical modification method of Corvic is suggested, including having butadiene-based or the acrylic acid of rubber constituent
Esters latex particle carries out copolymerization, such as Chinese patent with vinyl chloride after the polymer of the upper esters of acrylic acid of grafting
The method that CN101775105B proposes, will vinyl chloride and " nuclear core " be low cross-linking esters of acrylic acid rubber polymer and
The polyacrylate latex particle of " shell " polymer for having relatively high glass transition temperature carries out copolymerization, thus prepares and can directly make
Corvic.Due in this technique as nuclear core polymer in the acrylate rubber polymer of impact-resistant modified component
The percent grafting of grafting (methyl) acrylate is not enough, and the polyvinyl chloride resin product mechanical property produced is relatively low, and uses in technique
The recovery method such as emulsion polymerization technique and spray drying, in final products, chemical impurity is more, dielectric properties can be poor, limit
Make range.Chinese patent CN1043427C refer to a kind of two step method and prepare impact-resistant polyacrylate/vinyl chloride
The method of graft copolymer, the first step first synthesizes by acrylate and the crosslinkable monomers copolymerization system containing two unconjugated double bonds
Becoming Polyacrylate Emulsion, second step carries out suspension graft copolymerization again, thus prepares the resin of shock resistance with vinyl chloride.
In this invention, when the crosslinkable monomers containing two unconjugated double bonds and acrylic ester copolymer, define equal phase structure, simultaneously can
Cross-linking monomer ensures that acrylate rubber has certain gel content mutually, as carrying out the raw material of copolymerization with vinyl chloride, and latex granule
The chloride graft active site that sub-surface is provided is the most not enough, thus the shock resistance of the naval stores obtained with chloroethylene copolymer
The mechanical performances such as intensity can not fully reflect the maximum contribution that acrylate rubber can provide mutually.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, it is provided that a kind of impact strength, good toughness
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer.For acrylate rubber grafted branches Vinyl Chloride Monomer process
The problem that middle acrylate rubber grafted branches active site is not enough, it is provided that the acrylate rubber latex of a kind of nucleocapsid structure prepares chlorine
The method of vinyl graft copolymer resin.
The technical solution adopted for the present invention to solve the technical problems is: the vinyl chloride graft copolymer that this height is toughness reinforcing, its
It is characterised by: formed by the vinyl chloride of mass fraction 90 ~ 99% and the acrylate rubber latex copolymerization of 1 ~ 10%；
Described acrylate rubber latex is the nuclear core by mass fraction 95.0 ~ 99.0% and mass fraction 1.0 ~ 5.0%
The nucleocapsid structure of shell composition, described nuclear core by the nuclear core crosslinkable monomers of mass fraction 0.5 ~ 5.0% and mass fraction 95 ~
99.5% acrylate monomer homogeneously cross-links and forms, and described shell is formed at the surface aggregate of nuclear core by shell crosslinkable monomers；
Described crosslinkable monomers contains two or more unconjugated double bonds；
Described acrylate monomer is that vitrification point is less than the alkyl chain of-20 DEG C acrylic acid containing 2 ~ 10 carbon atoms
The one of Arrcostab, two or more mixture；The mean diameter of described acrylate rubber latex is 0.08 ~ 0.50
μm。
Preferably, the mean diameter of described acrylate rubber latex is 0.10 ~ 0.30 μm.
Described acrylate monomer is butyl acrylate.
Preferably, described acrylate monomer is 78 ~ 100% butyl acrylate and the ethyl acrylate of 0 ~ 22%, propylene
Acid n-propyl, 2-EHA, 1-Octyl acrylate, benzyl acrylate or the mixture of the many ether-ethers of acrylic acid.And this
Several alkyl acrylates are more preferable with the compatibility of butyl acrylate, energy when being polymerized with the crosslinkable monomers of selected independent copolymerization
Promote that reaction is uniform mutually, form the homogeneous cross-linked structure being suitable for.
Described nuclear core crosslinkable monomers is divinylbenzene, ethylene glycol dimethacrylate, BDO dimethyl
Acrylate, allyl methacrylate, allyl acrylate, diallyl phthalate, triallyl cyanurate
A kind of, the mixture of two or more arbitrary proportion.
Divinylbenzene, the ethylene glycol dimethacrylate of polyester compounds, BDO dimethyl allene
Acid esters, the crosslinkable monomers of unsaturated carboxylic acid class: allyl methacrylate, allyl acrylate, diallyl and three allyls
Base class: diallyl phthalate, triallyl cyanurate, cross-linking monomer can similar be used alone or variety classes is joined
Close and use.The crosslinkable monomers participating in copolymerization need to carry out copolymerization with acrylate, good to acrylate adaptability, can be retained in again
The active grafting site that surface is enough.
Described shell crosslinkable monomers is allyl methacrylate, diallyl phthalate or maleic acid two allyl
Ester.The crosslinkable monomers of independent copolymerization is polymerized formation shell with the double bond active site on the polymer emulsion surface of homogeneous crosslinking, both
To there is provided enough double bond active site for latex, to have enough compatibilitys with the Vinyl Chloride Monomer of graft copolymerization again.
The preparation method of the vinyl chloride graft copolymer that a kind of above-mentioned height is toughness reinforcing, it is characterised in that: graft copolymerization is divided into
In two stages, the first stage is the rich surface prepared and the have nucleocapsid structure acrylate rubber containing unsaturated double-bond activity grafting site
Glue latex, first passes through emulsion polymerization and can be handed over the nuclear core containing two or more unconjugated double bonds by acrylate monomer
The polymer emulsion of the homogeneous crosslinking of connection monomer copolymerization preparation is as nuclear core, then passes through shell on the particle surface of polymer emulsion
Crosslinkable monomers polymerization forms shell；Second stage is the acrylate rubber that rich surface contains unsaturated double-bond activity grafting site
Latex and vinyl chloride carry out graft copolymerization.
Described preparation has the rich surface acrylate rubber latex containing unsaturated double-bond activity grafting site of nucleocapsid structure
Method particularly includes:
1) in the reactor be furnished with reflux condenser, 100 ~ 500 weight portion desalted waters, 0.5 ~ 5.0 weight portion nuclear core are added
Crosslinkable monomers, 90 ~ 99.5 parts by weight propylene acid esters monomers and other auxiliary agent are stirred, and are warming up to 68 ~ 72 DEG C, simultaneously to still
Inside it is blown into nitrogen, replaces oxygen therein, and be incubated 10 minutes, be subsequently adding initiator and start polymerization, after reacting 2 hours, system
Obtain the acrylate rubber latex nuclear core of internal homogeneous crosslinking；
2) polymer emulsion particle surface polymerization: in reactor add 1.0 ~ 5.0 weight portion shell crosslinkable monomers,
Initiator, desalted water, successive reaction 1 hour, after detection final conversion of monomer arrives 99.5%, latex solid content is 10 ~ 50%,
Prepare the rich surface acrylate rubber latex with nucleocapsid structure containing unsaturated activity double key.
Preferably, described preparation has the rich surface acrylate rubber containing unsaturated double-bond activity grafting site of nucleocapsid structure
Glue latex method particularly includes:
1) synthesis seed latex: in the reactor be furnished with reflux condenser add 100 ~ 500 weight portion desalted waters and its
Its auxiliary agent is stirred, and 0.5 ~ 5.0 weight portion nuclear core crosslinkable monomers and 90 ~ 99.5 parts by weight propylene acid esters monomers is mixed,
Take in 1/20 ~ 1/3 addition reactor of mixture, be warming up to 68 ~ 72 DEG C, in still, be blown into nitrogen simultaneously, replace oxygen therein
Gas, and it is incubated 10 minutes, it is subsequently adding initiator and starts polymerization, after reacting 1 hour, prepare the seed glue of internal homogeneous crosslinking
Breast；
2) expanding: in the way of disposable addition, continuously dropping or segmentation addition, in reactor, to add remaining nuclear core
Crosslinkable monomers and the mixture of acrylate monomer, continue emulsion polymerization and carry out expanding, prepare the acrylic acid of required particle diameter
Ester rubber latex nuclear core；
3) polymer emulsion particle surface polymerization: in reactor add 1.0 ~ 5.0 weight portion shell crosslinkable monomers,
Initiator, desalted water, successive reaction 1 hour, after detection final conversion of monomer arrives 99.5%, latex solid content is 10 ~ 50%,
Prepare the rich surface acrylate rubber latex with nucleocapsid structure containing unsaturated activity double key.
The acrylate rubber latex of described small particle can add the acrylic latex containing carboxyl and carry out expanding, with
To big particle diameter and the acrylate rubber latex of bimodal distribution.
The described acrylate rubber latex that rich surface contains unsaturated double-bond activity grafting site connects with vinyl chloride
Branch copolymerization method particularly includes: in the reactor of evacuation removing oxygen, add 200 ~ 300 weight portion desalted waters, 1 ~ 10 weight portion
Acrylate rubber latex butt, 90 ~ 99 weight part of vinyl chloride monomers and other auxiliary agent, open stirring mixing 30 minutes after again
It is warming up at 35 ~ 65 DEG C carry out graft copolymerization；Prepare the graft copolymer of vinyl chloride and acrylate rubber, reaction controlling
The suspension polymerization reaction conversion ratio of vinyl chloride should be 75 ~ 95%, and the obtained vinyl chloride-base polymer degree of polymerization is 500 ~ 1500
Between.
In acrylate rubber latex, with acrylate carry out combined polymerization formed homogeneous cross-linked copolymer containing two
Or the mass ratio of two or more unconjugated double bond crosslinkable monomers is 0.5 ~ 5.0%.
In the present invention, the acrylate rubber latex particle surface being used for carrying out graft copolymerization with vinyl chloride should be rich
Containing double bond activity grafting site, and being formed by of this structure will be containing two or more unconjugated double bond crosslinkable monomers
Acrylate rubber latex particle surface homopolymerization polyreaction in homogeneous crosslinking completes and obtains, and only in this way guarantee exists
The surface of acrylate rubber latex particle provides grafting active site as much as possible.
The volume average particle size of the rubber phase latex particle of the acrylate that emulsion polymerization obtains is 0.08 ~ 0.50 μm, more
Preferably 0.10 ~ 0.30 μm.Synthesized acrylate rubber latex should have suitable mean diameter and particle size distribution.Flat
When all particle diameter is less than 0.08 μm, the crackle that rubber phase component produces for impact can not effectively terminate, and during more than 0.50 μm, single
The rubber phase amount of position weight can be not enough, and in a word, particle diameter is less than 0.08 μm and the chlorine more than the acrylate obtained by 0.50 μm
Ethylene suspension copolymer shock resistance and toughness all can be not enough.
Acrylate monomer emulsion is polymerized the initiator that used, can be water-soluble polymerization initiator, as potassium peroxydisulfate,
Ammonium persulfate .s etc., it is also possible to be oil soluble peroxides, such as the peroxide such as cyclohexanone peroxide etc. of ketone or aldehyde, diacyl mistake
Oxide such as peroxidating phenyl-diformyl, lauroyl peroxide etc., hydroperoxides such as hydrogen peroxide, isopropyl benzene hydroperoxide etc.,
And dialkyl peroxide, alkyl ester and azo polymerization initiator etc..The initiation of polyreaction both can be with thermal initiation
Polyreaction, it would however also be possible to employ oxidoreduction mode initiated polymerization.
Initiator amount is 0.05 ~ 0.5% mass ratio relative to acrylic ester polymerization monomer mass.
Acrylic acid ester emulsion polymerization emulsifying agent used can be anionic surfactant such as potassium palmitate, enuatrol,
The alkali metal salt of the fatty acids such as potassium stearate, the alkali metal salt of higher alcohol sulfate such as sodium lauryl sulphate etc., benzene sulfonamide
Acid or the alkali metal salt such as dodecylbenzene sodium sulfonate of alkyl naphthalene sulfonic acid, dodecyl sodium naphthalene sulfonate etc., naphthalenesulfonateformaldehyde formaldehyde is condensed
Thing sodium salt such as dioctyl sulfonic acid sodium succinate etc..Can also be nonionic surfactant, such as polyoxyethylene alkyl ether class
Polyoxyethylene lauryl ether etc., sorbitan fatty acid ester class such as sorbitan monostearate etc., fatty acid list is sweet
The glycerin mono-fatty acid ester etc. of grease class.Can also is that cationic surfactant and high molecular surfactant, also include the moon
Ion or cationic surfactant are applied in combination with nonionic surfactant, are not particularly limited in the present invention.
The preparation of described acrylate rubber latex can also add other auxiliary agents, stably make including polymerization system pH-value
PH dash adjustment agent, reduce in the water solublity strong acid and strong base inorganic salt of emulsifying agent critical micelle concentration and complex solution miscellaneous
The water soluble complexing agents etc. of matter.
During emulsion polymerization, latex system solid content is in the range of 10 ~ 50%, the most permissible in the range of 10 ~ 50%
It is met the acrylate rubber latex of requirement, but should not be higher than 50%, otherwise the easy breakdown of emulsion of polymerization system forms blob of viscose and reduces receipts
Rate, the efficiency that solid content then reacts less than 10% is the lowest, the most uneconomical.The acrylate rubber latex finally given
When monomer conversion is more than 99.5%, polyreaction terminates.
For obtaining the chloride graft polymer of the present invention, the means such as emulsion polymerization, suspension polymerisation, polymerisation in bulk are the most permissible
Use.Producing convenience from process implementing and Product recycling etc. and economy point considers, suspension polymerisation is the most optimum life
Product means.
For obtaining the chloride graft polymeric articles of described acrylate, poly-with the grafting of final vinyl chloride acrylate
Compound 100 parts by weight calculate, and butt acrylate rubber latex wherein used accounts for 1 ~ 15 part, the Vinyl Chloride Monomer weight of polymerization
Amount number is 85 ~ 99 parts.The acrylate rubber latex being added 1 ~ 15 weight portion improves vinyl chloride graft copolymer resins
Physical and mechanical properties, such as shock strength, hot strength.
During the suspension polymerization of vinyl chloride, Vinyl Chloride Monomer based on 100 weight portions, desalted water used
Consumption is 100 ~ 500 weight portions.
Should use macromolecule dispersing agent in suspension polymerization, the dispersant used mainly serves for ensuring reaction system
Stability, coordinate suitable stirring condition (stirring paddle type and rotating speed etc.), can be used for controlling the shape of final resin particle and
Distribution.
Selected dispersant can be those conventional chloroethylene polymerization dispersants, as polyvinyl alcohol, hydroxyethyl cellulose,
Hydroxypropyl methyl cellulose, methylcellulose, sodium polyacrylate, polyacrylamide, maleic acid alkyl vinyl ether polymers etc..
Vinyl Chloride Monomer based on 100 weight portions, the consumption of dispersant should be 0.1 ~ 0.9 weight portion, preferably 0.15 ~ 0.50 weight
Part, in this range, grain diameter size and the graft resin product of distribution satisfaction all can be obtained.
The initiator that suspension polymerization of VC is used should preferred oil-soluble initiator, and be readily dissolved in chloroethene
In alkene, the example of these initiators has peroxidating two acyl, such as dilauroyl peroxide, dibenzoyl peroxide；Peroxide esters, as
Tert-Butyl peroxypivalate etc.；Dialkyl, such as cumyl peroxide etc.；Dialkyl peroxydicarbonates class,
Such as peroxy dicarbonate isopropyl phenyl ester etc.；Azo, such as 2,2'-Azobis(2,4-dimethylvaleronitrile) etc..
In the present invention, vinyl chloride is 35 ~ 65 with the suspension polymerization reaction temperature of acrylate rubber latex (A)
DEG C, the obtained vinyl chloride-base polymer degree of polymerization is between 500 ~ 1500.
If it is required, in the suspension polymerization reaction system of vinyl chloride, it is also possible to add other auxiliary agents, bag further
Include the one or more of which additives such as molecular weight regulator, pH regulator, metal chelating agent.
The suspension polymerization reaction conversion ratio of vinyl chloride should be 75 ~ 95%(based on the vinyl chloride gross mass added), too high
Then the reactive polymeric time needs to extend, and the economy of production is bad, and conversion ratio is less than 75%, then the monomer removal time is more, remaining
Vinyl Chloride Monomer the most more, resin thermal stability is poor.
In chloride graft polyreaction when reaching desired conversion ratio, the unreacted monomer in slurry is removed, warp
Crossing centrifuge dewatering, wet feed the most i.e. can obtain the vinyl chloride graft copolymer product of acrylate of the present invention.
Compared with prior art, a kind of high toughness reinforcing vinyl chloride graft copolymer of the present invention and preparation method thereof is had
Provide the benefit that: the vinyl chloride graft copolymer resins that the present invention prepares has the erosion-resisting characteristics of excellence and good toughness.
With general surface without compared with the copolymer product of the acrylate rubber latex grafting vinyl chloride of grafting active site, according to the present invention
Graft copolymer resin prepared by method is distributed in vinyl chloride granule acrylate rubber uniform particle, and provides
Higher impact strength, the excellent in workability of graft copolymer resin, and need not use extra impact modifier.This
Polymer can directly be processed manufacturing the resin that shock resistance is excellent.
Detailed description of the invention
Do below by specific embodiment high toughness reinforcing vinyl chloride graft copolymer a kind of to the present invention and preparation method thereof
Further illustrate.Wherein embodiment 1 is most preferred embodiment.
1. the analysis test method employed in embodiment and comparative example
Latex particle size Malvern Mastersizer 2000
Simply supported beam notch impact strength GB/T 1043.1-2008
Stretching yield stress GB/T 1040-2006
2. chloroethylene copolymer resin processing formula and condition
Graft copolymer resin job evaluation formula
Chloroethylene copolymer resin 100 parts
Organotin 17MOK-N 2.0 parts
Calcium stearate 0.6 part
Lubricant ZB-60 0.6 part
Lubricant ZB-74 0.4 part
Gained chloroethylene copolymer resin is prepared material by above-mentioned formula, mixes in high-speed mixer, then exist
Carrying out mixing action, twin-roll mixing temperature 175 ± 5 DEG C on SK-160B double roll mill, mixing time is 5 minutes, pulls out sheet
Material, then suppresses the thick sheet material of 4mm on hot press, and press temperature 180 ± 2 DEG C, the press time is 3 minutes, the sheet material of compacting
Make Charpy Impact batten and tensile property test bars according to standard-required, under normal temperature condition, carry out performance test.
Embodiment 1
(1) preparation of acrylate rubber latex (A1)
Acrylate rubber nuclear core prepares formula
Butyl acrylate 96.5 parts
Divinylbenzene 0.5 part
Sodium lauryl sulphate 0.45 part
Potassium peroxydisulfate 0.35 part
Desalted water 245 parts
To 1000mL be furnished with in the glass reaction still of reflux condenser addition desalted water, emulsifier sodium lauryl sulfate with
And it is mixed with the Butyl Acrylate Monomer of divinylbenzene, and open stirring, be warming up to 70 DEG C, in still, be blown into nitrogen simultaneously, displacement
Oxygen therein, and keep 10 minutes at 70 DEG C, in still, then add the initiator solution dissolved with potassium peroxydisulfate, cause
Polymerization, after reacting 2.0 hours, sampling, solution has changed into the emulsion of inclined blue, the volume average particle size that particle instrument records
0.117 μm, monomer conversion 99.7%, prepare the acrylate rubber nuclear core latex of internal homogeneous crosslinking.
The material of following formula is added again in glass reaction still.
Hud typed acrylic ester polymerization formula
Allyl methacrylate 3.0 parts
Potassium peroxydisulfate 0.05 part
Desalted water 5.0 parts
Measuring final conversion of monomer after reacting 1 hour is 99.5%, latex solid content 29.0%, latex volume average particle
Footpath is 0.119 μm, and butyl acrylate accounts for 96.5% mass ratio relative to the butt of acrylate rubber latex, and prepared rich surface contains
The acrylate rubber latex (A1) with nucleocapsid structure of unsaturated activity double key.
(2) vinyl chloride is prepared with the graft copolymer (B1) of acrylate rubber
Based on the acrylate rubber latex of above-mentioned final preparation, carry out the suspension polymerization of following formula.
Chloride graft polymerization formula
Desalted water 250 parts
Acrylate rubber latex (A1) 5.0 parts (butt)
97.0 parts of vinyl chloride
Polyvinyl alcohol KH-20 0.05 part
HPMC E50 0.18 part
Peroxidating neopentanoic acid tert-pentyl ester 0.15 part
Above-mentioned desalted water, acrylate rubber latex is added in the 10L stainless steel cauldron of extracting vacuum removing oxygen
(A1), polyvinyl alcohol KH-20, HPMC E50, peroxidating neopentanoic acid tert-pentyl ester and Vinyl Chloride Monomer, unlatching
Stirring mixing is warming up at 62 DEG C reaction after 30 minutes again, and 2 mercapto ethanol is continuously added to polymeric kettle in 90 minutes after reaction starts
In, reaction, until pressure drop only reaches 0.20MPa (relative initial pressure), adds diethyl hydroxylamine, removes reacted vinyl chloride
Monomer, pulp centrifuged dehydration, gained wet feed is dried under the conditions of 60 DEG C, obtains the acrylate graft copolymers of chloride graft
Powder, wherein acrylate rubber latex (butt) content is that 6.6%(is relative to chloride graft polymer quality).Gained powder
Material is processed sample preparation according to the processing test formulations of aforementioned vinyl chloride graft copolymer, and carries out measuring mechanical property, gained
Result is listed in table 1.
Embodiment 2
The preparation method of the rich surface acrylate rubber latex (A2) with nucleocapsid structure containing activity double key is with implementing
Example 1, it is the most same as in Example 1 with the graft polymerization procedure of vinyl chloride, except that carry out graft copolymerization with vinyl chloride
The consumption of acrylate rubber latex (A2) (butt) is 4.0 parts, the copolymer of final chloride graft acrylate rubber
(B2) in product, acrylate rubber phase mass fraction is 4.8%, and products obtained therefrom is processed test, and result is listed in table 1.
Embodiment 3
The preparation method of the rich surface acrylate rubber latex (A3) with nucleocapsid structure containing activity double key is with implementing
Example 1, it is the most same as in Example 1 with the graft polymerization procedure of vinyl chloride, except that carry out graft copolymerization with vinyl chloride
The consumption of acrylate rubber latex (A3) (butt) is 9.0 parts, the copolymer of final chloride graft acrylate rubber
(B3) in product, acrylate rubber phase mass fraction is 10.2%, and products obtained therefrom is processed test, and result is listed in table 1.
Embodiment 4
The preparation method of the rich surface acrylate rubber latex (A4) with nucleocapsid structure containing activity double key is with implementing
Example 1, except that butyl acrylate is 96 parts, the crosslinkable monomers diallyl phthalate of copolymerization is 1.0 parts, gained
The rich surface acrylate rubber latex containing double bond grafting site is the most same as in Example 1 with the graft polymerization procedure of vinyl chloride.?
In copolymer (B4) product of whole chloride graft acrylate rubber, acrylate rubber phase mass fraction is 6.2%, by gained
Product is processed test, and result is listed in table 1.
Embodiment 5
The preparation method of the rich surface acrylate rubber latex (A5) with nucleocapsid structure containing activity double key is with implementing
Example 1, except that butyl acrylate is 96 parts, the crosslinkable monomers BDO dimethylacrylate of copolymerization is 2.0
Part, the crosslinkable monomers of last individually grafting is dially phthalate, and consumption is 2.0 parts, and gained rich surface connects containing double bond
The acrylate rubber latex of scolus is the most same as in Example 1 with the graft polymerization procedure of vinyl chloride.Final chloride graft third
In copolymer (B5) product of olefin(e) acid ester rubber, acrylate rubber phase mass fraction is 6.5%, is processed products obtained therefrom surveying
Examination, result is listed in table 1.
Embodiment 6
The preparation method of the rich surface acrylate rubber latex (A6) with nucleocapsid structure containing activity double key is with implementing
Example 1, except that butyl acrylate replaces with 19 parts of methacrylic acid 2 Octyl Nitrites and the mixing of 77 parts of butyl acrylate
Thing, the diallyl phthalate of the crosslinkable monomers of copolymerization 2.0 parts, the crosslinkable monomers of last individually grafting is 2.0 parts
Diallyl maleate, the glycerol polymerization side of gained rich surface acrylate rubber latex and vinyl chloride containing double bond grafting site
Method is the most same as in Example 1.Acrylate rubber phase in copolymer (B6) product of final chloride graft acrylate rubber
Mass fraction is 6.5%, and products obtained therefrom is processed test, and result is listed in table 1.
Comparative example 1
The preparation method of acrylate rubber latex is prepared with the acrylate rubber latex of crosslinking homogeneous in embodiment 1,
Not carrying out the preparation manipulation of hud typed acrylate rubber latex, chloride graft method is the most identical.Gained acrylate rubber
Glue latex particle volume average particle size is 0.115 μm, acrylate polymer in final gained vinyl chloride suspension polymerization thing
Content is 6.2%.Gained powder is processed sample preparation according to the job evaluation test formulations of aforementioned vinyl chloride copolymer, and carries out
Measuring mechanical property, acquired results is listed in table 1.
Comparative example 2
The preparation method of the rich surface acrylate rubber latex containing double bond activity grafting site is with embodiment 5, different
Be butyl acrylate be 90 parts, the crosslinkable monomers BDO dimethylacrylate of copolymerization is 6.0 parts, the most individually connects
The crosslinkable monomers of branch is diallyl phthalate, and consumption is 4.0 parts, acrylate rubber latex and the grafting of vinyl chloride
Polymerization is the most same as in Example 5.Acrylate rubber in the copolymer product of final chloride graft acrylate rubber
Phase mass fraction is 6.4%, and products obtained therefrom is processed test, and result is listed in table 1.
Comparative example 3
The rich surface preparation method of the acrylate rubber latex with nucleocapsid structure containing activity double key with embodiment 5,
Except that butyl acrylate 85 parts, the diallyl phthalate of the crosslinkable monomers of copolymerization 8.0 parts, the most individually connect
The allyl methacrylate that crosslinkable monomers is 7.0 parts of branch, the gained rich surface acrylate rubber containing double bond grafting site
Latex is the most same as in Example 1 with the graft polymerization procedure of vinyl chloride.The copolymer of final chloride graft acrylate rubber
In product, acrylate rubber phase mass fraction is 6.5%, and products obtained therefrom is processed test, and result is listed in table 1.
Table 1
。
Embodiment 7
(1) synthesis of the nucleocapsid structure acrylate rubber latex (A7) of surface enrichment double bond active site
The synthesis of seed latex
Seed latex polymerization formula
Butyl acrylate 16.66 parts
2-EHA 2.94 parts
Diallyl phthalate 0.4 part
Sodium lauryl sulphate 0.10 part
Potassium peroxydisulfate 0.10 part
Desalted water 200 parts
To equipped with the 2000mL glass reaction still of reflux condensate device adds desalted water, emulsifying agent lauryl sulphate acid
Sodium and be mixed with the butyl acrylate of diallyl phthalate and the mix monomer of 2-EHA, unlatching is stirred
Mix, in still, be blown into nitrogen simultaneously, replace oxygen therein, and be warming up to 70 DEG C, under the conditions of 70 DEG C, keep logical nitrogen 10 minutes,
Then in still, add the initiator solution dissolved with potassium peroxydisulfate, cause polymerization, sample after 1 hour, record latex volume and put down
All particle diameter 0.115 μm, obtains seed latex.
Expanding polymerization
Continue up the material adding following formula in stating glass kettle.
Expanding polymerization formula
Butyl acrylate 66.64 parts
2-EHA 11.76 parts
Diallyl phthalate 1.6 parts
Sodium lauryl sulphate 0.12 part
Potassium peroxydisulfate 0.24 part
Desalted water 23.0 parts
Continue to drip continuously the above-mentioned butyl acrylate being mixed with diallyl phthalate and acrylic acid in glass kettle
The monomer mixture of 2-Octyl Nitrite, time for adding about 1.5 hours, simultaneously by the aqueous solution average mark 4 parts of potassium peroxydisulfate, monomer
Add portion when dropping starts, add portion every 30 minutes later.Lauryl sodium sulfate aqueous solution average mark three parts, from single
Body dropping starts to add portion every 30 minutes.After monomer dropping completes, continue reaction about 1 hour, thus prepare solid content
30.1%, the acrylate rubber latex of volume average particle size 0.189 μm.
Prepared by the rich surface nucleocapsid structure acrylate rubber latex containing activity double key
On the basis of expanding latex, feed by following formula.
Hud typed acrylic ester polymerization formula
Allyl methacrylate 3.0 parts
Potassium peroxydisulfate 0.05 part
Desalted water 10 parts
Allyl methacrylate, persulfate aqueous solution it is sequentially added in glass reaction still, after reacting 1 hour,
Still temperature bringing up to 80 DEG C and continues reaction 1 hour, it is 99 % that emulsion is polymerized final monomer conversion, and latex solid content is about
30.2%, latex volume average particle size is 0.191 μm, obtains the rich surface hud typed butyl acrylate) latex containing activity double key
(A7)。
(2) vinyl chloride is prepared with the graft copolymer (B7) of acrylate rubber
So that in (1), the rich surface of the preparation acrylate rubber latex (A7) containing double bond activity grafting site is as raw material, at 10L
Following formula polyreaction is carried out in stainless steel pressure reactor.
Chloride graft polymerization formula
Desalted water 250 parts
Acrylate rubber latex (A7) 8.0 parts (butt)
98.0 parts of vinyl chloride
HPMC E50 0.25 part
Peroxy dicarbonate double (2-Octyl Nitrite) 0.09 part
Above-mentioned desalted water, acrylate rubber latex is added in the 10L stainless steel cauldron of extracting vacuum removing oxygen
(A7), HPMC E50, peroxy dicarbonate double (2-Octyl Nitrite) and Vinyl Chloride Monomer, open stirring mixed
It is warming up at 57 DEG C reaction after closing 30 minutes again, until pressure drop reaches 0.20MPa (relative initial pressure), adds diethyl hydroxyl
Amine, removes reacted vinyl chloride monomer, pulp centrifuged dehydration, and gained wet feed is dried under the conditions of 60 DEG C, obtains chloride graft
Acrylate graft copolymers powder, wherein acrylate rubber latex (butt) content is that 9.3%(connects relative to vinyl chloride
Branch polymer quality).Gained powder is processed sample preparation according to the processing test formulations of aforementioned vinyl chloride graft copolymer, goes forward side by side
Row measuring mechanical property, acquired results is listed in table 2.
Embodiment 8
The preparation method of the rich surface acrylate rubber latex (A8) with nucleocapsid structure containing activity double key is with implementing
Example 7, except that the consumption of the mixture of 2-EHA and butyl acrylate is respectively 16.5 parts and 58 parts, altogether
It is 1.1 parts that poly-crosslinkable monomers replaces with BDO dimethylacrylate consumption, and the most individually grafting is cross-linking
Monomer is the diallyl phthalate of 5.0 parts, the gained rich surface acrylate rubber latex (A8) containing double bond grafting site
The most same as in Example 7 with the graft polymerization procedure of vinyl chloride, except for the difference that acrylate rubber latex (A8) consumption is 10 parts
(butt) vinyl chloride consumption is 90 parts.Acrylate rubber in copolymer (B8) product of final chloride graft acrylate rubber
Glue phase mass fraction is 10.8%, and products obtained therefrom is processed test, and result is listed in table 2.
Embodiment 9
(1) synthesis of the nucleocapsid structure acrylate rubber latex (A9) of surface enrichment double bond active site
The synthesis of seed latex
Seed latex polymerization formula
Butyl acrylate 4.5 parts
Diallyl phthalate 0.25 part
Sodium lauryl sulphate 0.10 part
Potassium peroxydisulfate 0.10 part
Desalted water 200 parts
To equipped with the 2000mL glass reaction still of reflux condensate device adds desalted water, emulsifying agent lauryl sulphate acid
Sodium and be mixed with the butyl acrylate of diallyl phthalate and the mix monomer of 2-EHA, unlatching is stirred
Mix, in still, be blown into nitrogen simultaneously, replace oxygen therein, and be warming up to 70 DEG C, under the conditions of 70 DEG C, keep logical nitrogen 10 minutes,
Then in still, add the initiator solution dissolved with potassium peroxydisulfate, cause polymerization, sample after 1 hour, record latex volume and put down
All particle diameter 0.05 μm, obtains seed latex.
Expanding polymerization
Continue up the material adding following formula in stating glass kettle.
Expanding polymerization formula
Butyl acrylate 90 parts
Diallyl phthalate 4.75 parts
Sodium lauryl sulphate 0.12 part
Potassium peroxydisulfate 0.24 part
Desalted water 23.0 parts
Continue to drip continuously the above-mentioned butyl acrylate being mixed with diallyl phthalate and acrylic acid in glass kettle
The monomer mixture of 2-Octyl Nitrite, time for adding about 1.5 hours, simultaneously by the aqueous solution average mark 4 parts of potassium peroxydisulfate, monomer
Add portion when dropping starts, add portion every 30 minutes later.Lauryl sodium sulfate aqueous solution average mark three parts, from single
Body dropping starts to add portion every 30 minutes.After monomer dropping completes, continue reaction about 1 hour, thus prepare solid content
13%, the acrylate rubber latex of volume average particle size 0.47 μm.
Prepared by the rich surface nucleocapsid structure acrylate rubber latex containing activity double key
On the basis of expanding latex, feed by following formula.
Hud typed acrylic ester polymerization formula
Diallyl maleate 1.0 parts
Potassium peroxydisulfate 0.05 part
Desalted water 10 parts
Allyl methacrylate, persulfate aqueous solution it is sequentially added in glass reaction still, after reacting 1 hour,
Still temperature bringing up to 80 DEG C and continues reaction 1 hour, it is 99 % that emulsion is polymerized final monomer conversion, and latex solid content is about
30.2%, latex volume average particle size is 0.49 μm, obtains the rich surface hud typed butyl acrylate) latex containing activity double key
(A9)。
(2) vinyl chloride is prepared with the graft copolymer (B9) of acrylate rubber
So that in (1), the rich surface of the preparation acrylate rubber latex (A9) containing double bond activity grafting site is as raw material, at 10L
Following formula polyreaction is carried out in stainless steel pressure reactor.
Chloride graft polymerization formula
Desalted water 250 parts
Acrylate rubber latex (A9) 1.0 parts (butt)
99.0 parts of vinyl chloride
HPMC E50 0.25 part
Peroxy dicarbonate double (2-Octyl Nitrite) 0.09 part
Above-mentioned desalted water, acrylate rubber latex is added in the 10L stainless steel cauldron of extracting vacuum removing oxygen
(A9), HPMC E50, peroxy dicarbonate double (2-Octyl Nitrite) and Vinyl Chloride Monomer, open stirring mixed
It is warming up at 57 DEG C reaction after closing 30 minutes again, until pressure drop reaches 0.20MPa (relative initial pressure), adds diethyl hydroxyl
Amine, removes reacted vinyl chloride monomer, pulp centrifuged dehydration, and gained wet feed is dried under the conditions of 60 DEG C, obtains chloride graft
Acrylate graft copolymers powder, wherein acrylate rubber latex (butt) content is that 1.1%(connects relative to vinyl chloride
Branch polymer quality).Gained powder is processed sample preparation according to the processing test formulations of aforementioned vinyl chloride graft copolymer, goes forward side by side
Row measuring mechanical property, acquired results is listed in table 2.
Embodiment 10
(1) synthesis of the nucleocapsid structure acrylate rubber latex (A10) of surface enrichment double bond active site
The synthesis of seed latex
Seed latex polymerization formula
Butyl acrylate 31 parts
Diallyl phthalate 1.0 parts
Sodium lauryl sulphate 0.10 part
Potassium peroxydisulfate 0.10 part
Desalted water 200 parts
To equipped with the 2000mL glass reaction still of reflux condensate device adds desalted water, emulsifying agent lauryl sulphate acid
Sodium and be mixed with the butyl acrylate of diallyl phthalate and the mix monomer of 2-EHA, unlatching is stirred
Mix, in still, be blown into nitrogen simultaneously, replace oxygen therein, and be warming up to 70 DEG C, under the conditions of 70 DEG C, keep logical nitrogen 10 minutes,
Then in still, add the initiator solution dissolved with potassium peroxydisulfate, cause polymerization, sample after 1 hour, record latex volume and put down
All particle diameter 0.211 μm, obtains seed latex.
Expanding polymerization
Continue up the material adding following formula in stating glass kettle.
Expanding polymerization formula
Butyl acrylate 62 parts
Diallyl phthalate 2.0 parts
Sodium lauryl sulphate 0.12 part
Potassium peroxydisulfate 0.24 part
Desalted water 23.0 parts
Continue to drip continuously the above-mentioned butyl acrylate being mixed with diallyl phthalate and acrylic acid in glass kettle
The monomer mixture of 2-Octyl Nitrite, time for adding about 1.5 hours, simultaneously by the aqueous solution average mark 4 parts of potassium peroxydisulfate, monomer
Add portion when dropping starts, add portion every 30 minutes later.Lauryl sodium sulfate aqueous solution average mark three parts, from single
Body dropping starts to add portion every 30 minutes.After monomer dropping completes, continue reaction about 1 hour, thus prepare solid content
45%, the acrylate rubber latex of volume average particle size 0.382 μm.
Prepared by the rich surface nucleocapsid structure acrylate rubber latex containing activity double key
On the basis of expanding latex, feed by following formula.
Hud typed acrylic ester polymerization formula
Diallyl maleate 5.0 parts
Potassium peroxydisulfate 0.05 part
Desalted water 10 parts
Allyl methacrylate, persulfate aqueous solution it is sequentially added in glass reaction still, after reacting 1 hour,
Still temperature bringing up to 80 DEG C and continues reaction 1 hour, it is 99 % that emulsion is polymerized final monomer conversion, and latex solid content is about
30.2%, latex volume average particle size is 0.391 μm, obtains the rich surface hud typed butyl acrylate) latex containing activity double key
(A10)。
(2) vinyl chloride is prepared with the graft copolymer (B10) of acrylate rubber
With the rich surface of the preparation acrylate rubber latex (A10) containing double bond activity grafting site in (1) as raw material,
Following formula polyreaction is carried out in 10L stainless steel pressure reactor.
Chloride graft polymerization formula
Desalted water 250 parts
Acrylate rubber latex (A10) 1.0 parts (butt)
99.0 parts of vinyl chloride
HPMC E50 0.25 part
Peroxy dicarbonate double (2-Octyl Nitrite) 0.09 part
Above-mentioned desalted water, acrylate rubber latex is added in the 10L stainless steel cauldron of extracting vacuum removing oxygen
(A10), HPMC E50, peroxy dicarbonate double (2-Octyl Nitrite) and Vinyl Chloride Monomer, open stirring mixed
It is warming up at 57 DEG C reaction after closing 30 minutes again, until pressure drop reaches 0.20MPa (relative initial pressure), adds diethyl hydroxyl
Amine, removes reacted vinyl chloride monomer, pulp centrifuged dehydration, and gained wet feed is dried under the conditions of 60 DEG C, obtains chloride graft
Acrylate graft copolymers powder, wherein acrylate rubber latex (butt) content is that 1.1%(connects relative to vinyl chloride
Branch polymer quality).Gained powder is processed sample preparation according to the processing test formulations of aforementioned vinyl chloride graft copolymer, goes forward side by side
Row measuring mechanical property, acquired results is listed in table 2.
Embodiment 11
(1) synthesis of the nucleocapsid structure acrylate rubber latex (A11) of surface enrichment double bond active site
The synthesis of seed latex
Seed latex polymerization formula
Butyl acrylate 13 parts
Diallyl phthalate 0.7 part
Sodium lauryl sulphate 0.10 part
Potassium peroxydisulfate 0.10 part
Desalted water 200 parts
To equipped with the 2000mL glass reaction still of reflux condensate device adds desalted water, emulsifying agent lauryl sulphate acid
Sodium and be mixed with the butyl acrylate of diallyl phthalate and the mix monomer of 2-EHA, unlatching is stirred
Mix, in still, be blown into nitrogen simultaneously, replace oxygen therein, and be warming up to 70 DEG C, under the conditions of 70 DEG C, keep logical nitrogen 10 minutes,
Then in still, add the initiator solution dissolved with potassium peroxydisulfate, cause polymerization, sample after 1 hour, record latex volume and put down
All particle diameter 0.193 μm, obtains seed latex.
Expanding polymerization
Continue up the material adding following formula in stating glass kettle.
Expanding polymerization formula
Butyl acrylate 80 parts
Diallyl phthalate 2.4 parts
Sodium lauryl sulphate 0.12 part
Potassium peroxydisulfate 0.24 part
Desalted water 23.0 parts
Continue to drip continuously the above-mentioned butyl acrylate being mixed with diallyl phthalate and acrylic acid in glass kettle
The monomer mixture of 2-Octyl Nitrite, time for adding about 1.5 hours, simultaneously by the aqueous solution average mark 4 parts of potassium peroxydisulfate, monomer
Add portion when dropping starts, add portion every 30 minutes later.Lauryl sodium sulfate aqueous solution average mark three parts, from single
Body dropping starts to add portion every 30 minutes.After monomer dropping completes, continue reaction about 1 hour, thus prepare solid content
45%, the acrylate rubber latex of volume average particle size 0.375 μm.
Prepared by the rich surface nucleocapsid structure acrylate rubber latex containing activity double key
On the basis of expanding latex, feed by following formula.
Hud typed acrylic ester polymerization formula
Diallyl maleate 5 parts
Potassium peroxydisulfate 0.05 part
Desalted water 10 parts
Allyl methacrylate, persulfate aqueous solution it is sequentially added in glass reaction still, after reacting 1 hour,
Still temperature bringing up to 80 DEG C and continues reaction 1 hour, it is 99 % that emulsion is polymerized final monomer conversion, and latex solid content is about
30.2%, latex volume average particle size is 0.409 μm, obtains the rich surface hud typed butyl acrylate) latex containing activity double key
(A11)。
(2) vinyl chloride is prepared with the graft copolymer (B11) of acrylate rubber
With the rich surface of the preparation acrylate rubber latex (A11) containing double bond activity grafting site in (1) as raw material,
Following formula polyreaction is carried out in 10L stainless steel pressure reactor.
Chloride graft polymerization formula
Desalted water 250 parts
Acrylate rubber latex (A11) 1.0 parts (butt)
99.0 parts of vinyl chloride
HPMC E50 0.25 part
Peroxy dicarbonate double (2-Octyl Nitrite) 0.09 part
Above-mentioned desalted water, acrylate rubber latex is added in the 10L stainless steel cauldron of extracting vacuum removing oxygen
(A10), HPMC E50, peroxy dicarbonate double (2-Octyl Nitrite) and Vinyl Chloride Monomer, open stirring mixed
It is warming up at 57 DEG C reaction after closing 30 minutes again, until pressure drop reaches 0.20MPa (relative initial pressure), adds diethyl hydroxyl
Amine, removes reacted vinyl chloride monomer, pulp centrifuged dehydration, and gained wet feed is dried under the conditions of 60 DEG C, obtains chloride graft
Acrylate graft copolymers powder, wherein acrylate rubber latex (butt) content is that 1.1%(connects relative to vinyl chloride
Branch polymer quality).Gained powder is processed sample preparation according to the processing test formulations of aforementioned vinyl chloride graft copolymer, goes forward side by side
Row measuring mechanical property, acquired results is listed in table 2.
Comparative example 4
The preparation method of acrylate rubber latex is prepared with the acrylate rubber latex of crosslinking homogeneous in embodiment 7,
Rich surface is not had to contain the nucleocapsid structure acrylate rubber latex preparation manipulation of activity double key, vinyl chloride suspension polymerization formula
Identical with operation.In the copolymer product of final chloride graft acrylate rubber, acrylate rubber phase mass fraction is
6.9%, gained chloroethylene copolymer product is processed test according to aforementioned formula and process conditions, result is listed in table 2..
Table 2
。
From the performance of Tables 1 and 2 detects, can be seen that ratio of the present invention with reference to each embodiment with comparative example 1 and comparative example 4
The simply supported beam notch impact strength and the elongation at break that are formed without the situation of nucleocapsid structure at acrylate rubber latex have
The biggest raising.With reference to each embodiment and comparative example 2 and comparative example 3 it can be seen that in the case of beyond proportioning of the present invention
Even if preparing the acrylate rubber latex of nucleocapsid structure, also will not have good simply supported beam notch impact strength and fracture is stretched
Long rate.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, appoints
What those skilled in the art changed possibly also with the technology contents of the disclosure above or be modified as equivalent variations etc.
Effect embodiment.But every without departing from technical solution of the present invention content, the technical spirit of the foundation present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.
Claims (9)
1. the preparation method of one kind high toughness reinforcing vinyl chloride graft copolymer, it is characterised in that: graft copolymerization is divided into two stages,
First stage is the rich surface prepared and the have nucleocapsid structure acrylate rubber latex containing unsaturated double-bond activity grafting site, first
First pass through emulsion polymerization by acrylate monomer with the nuclear core crosslinkable monomers containing two or more unconjugated double bonds altogether
The polymer emulsion of the homogeneous crosslinking of poly-preparation is as nuclear core, then passes through the cross-linking list of shell on the particle surface of polymer emulsion
Body polymerization forms shell；Second stage is that rich surface contains acrylate rubber latex and the chlorine of unsaturated double-bond activity grafting site
Ethylene carries out graft copolymerization.
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer the most according to claim 1, it is characterised in that: institute
State preparation and there is the concrete grammar of the rich surface of the nucleocapsid structure acrylate rubber latex containing unsaturated double-bond activity grafting site
For:
1) add 100 ~ 500 weight portion desalted waters in the reactor be furnished with reflux condenser, 0.5 ~ 5.0 weight portion nuclear core can be handed over
Receipts or other documents in duplicate body, 90 ~ 99.5 parts by weight propylene acid esters monomers and other auxiliary agent are stirred, and are warming up to 68 ~ 72 DEG C, blow in still simultaneously
Enter nitrogen, replace oxygen therein, and be incubated 10 minutes, be subsequently adding initiator and start polymerization, after reacting 2 hours, in preparing
The acrylate rubber latex nuclear core that portion homogeneously cross-links；
2) the particle surface polymerization of polymer emulsion: add 1.0 ~ 5.0 weight portion shell crosslinkable monomers, initiation in reactor
Agent, desalted water, successive reaction 1 hour, after detection final conversion of monomer arrives 99.5%, latex solid content is 10 ~ 50%, prepares
Rich surface is containing the acrylate rubber latex with nucleocapsid structure of unsaturated activity double key.
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer the most according to claim 1, it is characterised in that: institute
State preparation and there is the concrete grammar of the rich surface of the nucleocapsid structure acrylate rubber latex containing unsaturated double-bond activity grafting site
For:
1) synthesis seed latex: add 100 ~ 500 weight portion desalted waters in the reactor be furnished with reflux condenser and other helps
Agent is stirred, and 0.5 ~ 5.0 weight portion nuclear core crosslinkable monomers and 90 ~ 99.5 parts by weight propylene acid esters monomers is mixed, takes mixed
In 1/20 ~ 1/3 addition reactor of compound, it is warming up to 68 ~ 72 DEG C, in still, is blown into nitrogen simultaneously, replaces oxygen therein, and
It is incubated 10 minutes, is subsequently adding initiator and starts polymerization, after reacting 1 hour, prepare the seed latex of internal homogeneous crosslinking；
2) expanding: adding remaining nuclear core in reactor in the way of disposable addition, continuously dropping or segmentation addition can hand over
Receipts or other documents in duplicate body and the mixture of acrylate monomer, continue emulsion polymerization and carry out expanding, prepare the acrylate rubber of required particle diameter
Glue latex nuclear core；
3) the particle surface polymerization of polymer emulsion: add 1.0 ~ 5.0 weight portion shell crosslinkable monomers, initiation in reactor
Agent, desalted water, successive reaction 1 hour, after detection final conversion of monomer arrives 99.5%, latex solid content is 10 ~ 50%, prepares
Rich surface is containing the acrylate rubber latex with nucleocapsid structure of unsaturated activity double key.
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer the most according to claim 1, it is characterised in that: institute
The acrylate rubber latex that rich surface contains unsaturated double-bond activity grafting site and the vinyl chloride stated carry out the tool of graft copolymerization
Body method is: add 200 ~ 300 weight portion desalted waters, 1 ~ 10 parts by weight propylene acid esters rubber in the reactor of evacuation removing oxygen
Glue latex butt, 90 ~ 99 weight part of vinyl chloride monomers and other auxiliary agent, it is warming up to 35 again after opening stirring mixing 30 minutes ~
Graft copolymerization is carried out at 65 DEG C；Prepare the graft copolymer of vinyl chloride and acrylate rubber, reaction controlling vinyl chloride
Suspension polymerization reaction conversion ratio should be 75 ~ 95%, and the obtained vinyl chloride-base polymer degree of polymerization is between 500 ~ 1500.
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer the most according to claim 1, it is characterised in that: institute
The mean diameter of the acrylate rubber latex stated is 0.10 ~ 0.30 μm.
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer the most according to claim 1, it is characterised in that: institute
The acrylate monomer stated is butyl acrylate.
The preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer the most according to claim 1, it is characterised in that: institute
The acrylate monomer stated is 78 ~ 100% butyl acrylate and the ethyl acrylate of 0 ~ 22%, n-propyl, acrylic acid 2-
The mixture of the many ether-ethers of Octyl Nitrite, 1-Octyl acrylate, benzyl acrylate or acrylic acid.
8., according to the preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer described in claim 1 or 3, its feature exists
In: described nuclear core crosslinkable monomers is divinylbenzene, ethylene glycol dimethacrylate, BDO dimethacrylate
Ester, allyl methacrylate, allyl acrylate, diallyl phthalate, the one of triallyl cyanurate, two
Plant or the mixture of two or more arbitrary proportion.
9., according to the preparation method of a kind of high toughness reinforcing vinyl chloride graft copolymer described in any one of claim 1 ~ 3, it is special
Levy and be: described shell crosslinkable monomers is allyl methacrylate, diallyl phthalate or maleic acid two allyl
Ester.
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| CN1059343A (en) * | 1990-08-31 | 1992-03-11 | 希尔斯股份公司 | The preparation method of impact-resistant polyacrylate/vinyl chloride graft copolymer |
| CN1418898A (en) * | 2002-11-14 | 2003-05-21 | 河北工业大学 | Process for preparing high shock-resistance polyacrylic ester composite particle grafted vinyl chloride emulsion resin |
| KR20100013443A (en) * | 2008-07-31 | 2010-02-10 | 금호석유화학 주식회사 | An acrylic impact modifier and a manufacturing method thereof |
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| CN1059343A (en) * | 1990-08-31 | 1992-03-11 | 希尔斯股份公司 | The preparation method of impact-resistant polyacrylate/vinyl chloride graft copolymer |
| CN1418898A (en) * | 2002-11-14 | 2003-05-21 | 河北工业大学 | Process for preparing high shock-resistance polyacrylic ester composite particle grafted vinyl chloride emulsion resin |
| KR20100013443A (en) * | 2008-07-31 | 2010-02-10 | 금호석유화학 주식회사 | An acrylic impact modifier and a manufacturing method thereof |
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