CN100354328C - Method for producing polyvinyl chloride special for high-impact-resisting building material product - Google Patents
Method for producing polyvinyl chloride special for high-impact-resisting building material product Download PDFInfo
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- CN100354328C CN100354328C CNB2004100895126A CN200410089512A CN100354328C CN 100354328 C CN100354328 C CN 100354328C CN B2004100895126 A CNB2004100895126 A CN B2004100895126A CN 200410089512 A CN200410089512 A CN 200410089512A CN 100354328 C CN100354328 C CN 100354328C
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Abstract
The present invention discloses high impact resistance polyvinyl chloride resin special for building materials and a preparation method thereof. A multi-step emulsion polymerization method is firstly used for preparing composite particle rubber latex of polyacrylic ester, and after the pH value of the composite rubber latex is regulated to 7, the composite rubber latex continues to be grafted and polymerized in a suspension mode with chloroethylene. Finally, a graft copolymer of the polyacrylic ester and the chloroethylene is prepared. The copolymer can be widely used for the field of plastic building material products having requirements for impact resistant performance, such as profiled bars, pipe materials, sheet materials, etc.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinyl chloride copolymer resins, relate in particular to the preparation method of the graft copolymer of a kind of polyacrylic ester and vinylchlorid grafting suspension polymerization.
Background technology
Improve polyvinyl chloride (PVC) RESINS (PVC) goods erosion-resisting characteristics, can take two kinds of methods of blend and copolymerization, blending and modifying is exactly to add toughner to improve the goods shock strength in the PVC course of processing; Modification by copolymerization then adopts grafting, method such as crosslinked to reach the purpose that improves the goods shock strength.
Modification by copolymerization can make between polyvinyl chloride and toughner and be connected with chemical bond, plays solubilizing agent by graft copolymer, and consistency improves, and toughening effect is better, material ageing-resistant, and processing characteristics is also higher.The mode that employing makes vinylchlorid graft copolymerization on the polyacrylic ester segment obtain high-impact PVC is improved the erosion-resisting characteristics of polyvinyl chloride resin, compare with blend method, graft copolymerization has its irreplaceable advantage, as it when keeping the character of trunk polymer, introduce the characteristic of branched chain polymer, also increased the consistency of two-phase system etc.
Introduced in CN1161345 by letex polymerization and make in the presence of acrylic acid series and the styrene copolymer latices slurry, the suspension polymerization height is transparent, the method for shock-resistant polyvinyl chloride (PVC) RESINS.But though the goods transparency significantly improves in this constituent, goods shock strength increase rate is little.Means such as employing seeded emulsion polymerization, organic agglomerant agglomeration and the adding of nano grade inorganic particle have been introduced among the patent CN1418898, make polyacrylic ester composite particles latex, grafting letex polymerization between latex and vinylchlorid makes the high rush-resistant polyvinyl chloride emulsion resin with multilayer core shell structure.But stick with paste resin because its product is PVC, can't be applied to PVC building material made fields such as profiled material, tubing, sheet material.
Summary of the invention
The technical issues that need to address of the present invention are the production methods that disclose a kind of polyvinyl chloride special for high-impact-resisting building material product, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
Adopt the multi-step emulsion polymerization method to make polyacrylic ester composite particles latex earlier, compounded latex continues to carry out suspension polymerization with vinylchlorid after potential of hydrogen is adjusted to neutrality, finally makes the graft copolymer of polyacrylic ester and vinylchlorid.This multipolymer can be widely used in profiled material, tubing, sheet material etc. have requirement to erosion-resisting characteristics materials for construction goods field.
Method of the present invention comprises the steps:
(1) preparation of polyacrylic ester compounded latex: carry out emulsion polymerization with the raw material that comprises following component and mass fraction at least, obtain a kind of compounded latex of nucleocapsid structure, wherein, the nuclear part is a polyacrylic ester, and shell partly is a polyalkyl acrylate:
Polymeric reaction temperature 70-90 ℃, the reaction times is 3.5～6.0 hours, obtains compounded latex, and carries out emulsion polymerization by following prescription:
The composition weight umber
Deionized water 100
Acrylate 30-45
Alkyl acrylate 5.0-20
Emulsifying agent 0.10-2.00
Initiator 0.05-0.75
Linking agent 0.10-2.00
(2) in above-mentioned compounded latex, add basic solution, regulate pH value to 6.0-9.0;
(3) compounded latex and vinyl chloride monomer graft polymerization:
With the compounded latex that step (2) makes, vinyl chloride monomer in the method grafting of employing suspension polymerization, react by following prescription:
The composition weight umber
Vinyl chloride monomer 100
Deionized water 150-250
Step (2) emulsion 15-30
Initiator 0.020-0.10
Dispersion agent 0.10-0.60
PH conditioning agent 0.010-0.050
Polymeric reaction temperature 40-60 ℃, the reaction times is 6.0～9.0 hours, promptly obtains vinyl chloride graft copolymer after centrifugal, drying.
Method of the present invention, in the step (1), acrylate is preferably butyl acrylate, and alkyl acrylate is preferably methyl methacrylate, and the weight ratio of acrylate and alkyl acrylate is 80～85: 15～20.
Said shell portion is an alkyl acrylate, the preferable methyl methyl acrylate, and the weight ratio of nuclear portion and shell portion is 80～85: 15～20 o'clock are better;
Acrylate preferably adopts adding in batches or drips mode continuously, so that can control latex particle size and distribution preferably, and easy temperature control;
Alkyl acrylate can adopt once feeding modes such as adding, drip continuously, first swelling is reacted again, wherein adopts the feeding mode of first swelling 0.5-1.0hr repolymerization, and is the most favourable to the formation of nucleocapsid structure;
The emulsifying agent that step of the present invention (1) polymerization is adopted is selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, nonionogenic tenside, preferably sodium dodecyl sulfate, consumption is that 0.10-2.00wt% (in deionized water weight) is better, be preferably 0.15-1.20wt%, emulsifying agent can once drop into before the nuclear polymerization, add respectively or replenish in batches or continuously in polymerization process also can be in synthetic kernel portion and shell portion the time and add, and adds latex particle size more easy to control during wherein with polymerization in batches or continuously and obtains nucleocapsid structure;
The initiator that step (1) polymerization is adopted is selected from thermolysis type or oxidation-reduction type, and thermolysis type initiator can be selected two kinds of peroxide and azo classes;
Preferred Potassium Persulphate of said peroxide initiator or ammonium persulphate etc.;
Preferred azo two isonitrile of said azo-initiator, azo two miaow base propane hydrochloride salt;
Wherein adopt Potassium Persulphate better;
Oxidation-reduction type initiator is selected from Potassium Persulphate-sodium hydrogen sulfite system, hydrogen phosphide cumene-formolation S-WAT system, hydrogen peroxide-ferrous salt system etc.;
Preferred hydrogen phosphide cumene-formolation S-WAT system.Initiator amount is that 0.10-2.00wt% (with the summation meter of acrylate and alkyl acrylate ester monomer) is better, is preferably 0.50-1.20wt%;
For making polyacrylic ester anti-impact effect reach best, the crosslinked situation influence between the degree of crosslinking size of nuclear and nuclear and the shell is huge.Polyacrylic ester nuclear degree of crosslinking size directly has influence on its elastic size, and making the appropriately crosslinked purpose of nuclear is in order to improve the polyacrylic acid ester elastomer, and then improves the toughness of polyvinyl chloride resin.The nuclear degree of crosslinking is too big, and the rigidity of polyacrylic ester is too big, the elasticity deficiency; Degree of crosslinking is too little, and polyacrylic ester viscosity is too big, and elasticity is also not enough, and when thermoforming the breaking of molecular chain easy slippage causing polyacrylic ester particle, be unfavorable for bringing out of crazing, do not have the effect of anti-impact.For reaching the crosslinked of polyacrylic ester nuclear appropriateness, can when polymerization, add crosslinked that linking agent realizes examining, the linking agent that contains two unsaturated double-bonds in the preferred molecule, as a kind of or its mixture in Vinylstyrene, butyleneglycol double methacrylate, Phthalic acid, diallyl ester, Ethylene glycol dimethacrylate or the diallyl maleate etc., preferred best especially with the linking agent effect that contains diallyl maleate, consumption is 0.5-2.0wt% (in an acrylate monomer weight), is preferably 1.0wt%.
It is 1～5% the aqueous solution that said alkaline matter is selected from mass concentrations such as sodium hydroxide, sodium bicarbonate, bicarbonate of ammonia or ammoniacal liquor, wherein selects ammoniacal liquor better; Alkaline matter can add in the latex building-up process, also can add behind end of synthesis, adds better in the synthetic back that is all over.
Said PH conditioning agent is selected from weakly alkaline materials such as bicarbonate of ammonia or sodium bicarbonate, chloroethylene polymerization is the process that constantly discharges hydrogenchloride, it is acid that system is easily, be reflected under the acidic conditions and carry out, the probability of using coarse particle increases, and kettle pasting matter also increases, and adds the weak base salt conditioning agent, can make the vinyl chloride graft copolymer particle more even, particle form is better.
Said dispersion agent is selected from the polyvinyl alcohol of partial alcoholysis, methylcellulose gum, ethyl cellulose, Vltra tears, polyacrylic acid, gelatin etc. wherein use polyvinyl alcohol (PVA) and Vltra tears (HPMC) better with the composite dispersing agent effect as the PVC polymerization.General polyvinyl alcohol (alcoholysis degree 75-85%, viscosity 20～60mPa.s), the Vltra tears (methoxy content 25～35% selected; Hydroxypropyl content 5～10%, viscosity is 35～60mpas), oil soluble polyvinyl alcohol (alcoholysis degree 35～65%, viscosity 2.0～10mPa.s) ternary compound dispersing agents, can coordinate and take into account the guarantor's glue ability and the dispersive ability of system, the coalescence and the dispersion of control drop guarantee that the interior porosity size of resin particle is even, eliminate macrobead and cross fine particle, it is narrow that size distribution becomes.Dispersant dosage is 0.10-0.60wt% (in a vinylchlorid weight), is preferably 0.20-0.40wt%.
Initiator can be selected organic peroxide evocating agent and azo-initiator for use in the step (3).Peroxide initiator can be benzoyl peroxide, the new enanthic acid tert-butyl ester of peroxidation, the special pentyl ester of peroxidation trimethylacetic acid, peroxide tert pivalate ester, peroxy dicarbonate be two-(2-ethylhexyl) etc., azo-initiator can be 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate etc.Its add-on is 0.02～0.10wt%
The add-on of emulsion can shock strength as required determine that the goods shock strength increases with the increase of emulsion add-on in the step (3), but increases with the emulsion add-on, and the tensile strength of goods descends.The general polyacrylate dispersion 4-8% that when suspension polymerization, adds (behind the emulsion conversion solid content to the vinyl chloride monomer weight ratio).
The mode of polyacrylic ester latex adding polymeric kettle can be initially just to drop in the still with deionized water, dispersion agent in the step (3), also can after monomer, water and dispersion agent adding stir, add in the still again, wherein a kind of adding mode in back is little to resin particle form influence, and uniform particles, polymerization-stable, sticking still are light.
Evaluation method:
Among the present invention following method is adopted in the evaluation of resin rerum natura:
(1) latex structures
The JEM-1200EXZ of Jeol Ltd. transmission electron microscope (TEM) test
(2) mean polymerisation degree
Measure according to the measuring method shown in the JISK 6721
(3) apparent density
Measure according to the measuring method shown in the JISK 6721
(4) resin particle
Determine median size and particle diameter distribution width with MALVERN MS-2000 particle diameter instrument
(5) notched Izod impact strength
Measure according to the measuring method shown in the GB/T1043-93
(6) tensile strength
Measure according to the measuring method shown in the GB/T1040-92
Adopt the polyvinyl chloride special for high-impact-resisting building material product of method preparation of the present invention, notched Izod impact strength can reach more than the 30.0KJ/m2, tensile strength can reach more than the 45.0KJ/m2, particle form is regular, distribute and concentrate, fine particle is few, and the sticking still of polymeric kettle is light, multipolymer can be widely used in profiled material, tubing, sheet material etc. has the materials for construction goods field of requirement to erosion-resisting characteristics, can satisfy the needs of making high-impact-resisting building material product fully.
Embodiment
Embodiment 1
The 1st step: polyacrylic ester compounded latex particle is synthetic:
Feed the high pure nitrogen deoxygenation in the 1L four-hole boiling flask of being furnished with electronic speed governing stirring, reflux exchanger and Electric heating bowl, continue to add deionized water 380ml, sodium lauryl sulphate 0.24g under the protection at nitrogen, startup is stirred 200rpm and is warming up to 85 ℃; The pre-emulsion 40ml that under this temperature, adds pre-configured butyl acrylate (BA)/linking agent diallyl maleate (DAM)/sodium lauryl sulphate (SLS)=192g/1.92g/0.72g), add Potassium Persulphate 0.50g, temperature control reaction 1 hour, drip remaining BA pre-emulsion and KPS solution 1.92g (4% concentration) continuously, reacted 2-3 hour, and examined partially polymerized end;
Cooling adds 48g methyl methacrylate monomer (BA/MMA feed ratio 80/20) and stirred swelling 0.5 hour, add sodium lauryl sulphate (KPS) solution 0.48g (4% concentration), be warming up to 85 ℃ and continue reaction 1-2 hour, after the insulation slaking, cooling discharging obtains compounded latex;
The 2nd step: with 5% concentration NH
3.H
2O titration compounded latex is regulated the compounded latex pH value between 7.0-9.0.
The 3rd step: the polyvinyl chloride graft copolymer resins is synthetic
Polyreaction is carried out in the 10L still of being furnished with stirring and chuck.Processing condition and process are summarized as follows: earlier with 4500ml deionized water, 0.40gNaHCO
3Pressed powder, PVA
1Dispersion agent 100ml, HPMC dispersion agent 100ml, PVA
2Dispersion agent 40ml drops in the still, pressure testing vacuumizes the back and adds vinyl chloride monomer 2000g, start and stirred 20 minutes, add the 120g polyacrylic ester latex with pump, remix stirred 20 minutes, add the initiator peroxy dicarbonate two-(2-ethylhexyl), be warming up to 57 ℃ of beginning polymerizations, keep polymerization temperature to reduce to 0.60Mpa, add 3ml terminator acetone semicarbazone thiocarbamide, push back discharging behind the receipts monomer certainly to polymerization pressure.Slurry obtains copolymer resins through centrifugal drying, the analytical test performance.
Above PVA
1Dispersion agent is an alcoholysis degree 80%, and viscosity is the polyvinyl alcohol of 48mPa.s; The HPMC dispersion agent is a methoxyl group substitution value 25%, hydroxypropyl substitution value 6%, the Vltra tears of viscosity 50mpa.s; PVA
2Dispersion agent is an alcoholysis degree 50%, the polyvinyl alcohol of viscosity 4.0mPa.s.
Test result: the TEM photo shows that polyacrylic ester latex possesses complete nucleocapsid structure, and shell thickness is more even.In temperature is under 23 ℃ of conditions, and it is 35KJ/m that mensuration grafting vinyl chloride copolymer resins makes the sample notched Izod impact strength
2, tensile strength 48.0 Mpa, particle form is regular, distributes to concentrate, and fine particle is few, and the sticking still of polymeric kettle is light, the results are shown in Table 1.
Embodiment 2
The butyl acrylate 144g that feeds intake when polyacrylic ester compounded latex particle is synthetic in the first step, the methyl methacrylate 96g that feeds intake, feed ratio 60/40, other technology is with implementing 1.(the results are shown in Table 1)
Embodiment 3
The butyl acrylate 168g that feeds intake when polyacrylic ester compounded latex particle is synthetic in the first step, the methyl methacrylate 72g that feeds intake, feed ratio 70/30, other technology is with implementing 1.(the results are shown in Table 1)
Embodiment 4
The butyl acrylate 216g that feeds intake when polyacrylic ester compounded latex particle is synthetic in the first step, the methyl methacrylate 24g that feeds intake, feed ratio 90/10, other technology is with implementing 1.(the results are shown in Table 1)
Table 1
Embodiment 5
Linking agent adopts diallyl maleate in the first step, consumption is 4% of a butyl acrylate, be made into pre-emulsion with butyl acrylate, sodium lauryl sulphate, the pre-emulsion of synthetic polyacrylic ester compounded latex particle (BA/DAM/SLS=192g/7.80g/0.72g), other technology is with implementing 1.(the results are shown in Table 2)
Embodiment 6
Linking agent Ethylene glycol dimethacrylate in the first step is made into pre-emulsion with butyl acrylate, sodium lauryl sulphate, synthetic polyacrylic ester compounded latex particle, and other technology is with implementing 1.(the results are shown in Table 2)
Embodiment 7
With different linking agent kinds, be made into pre-emulsion in the first step with butyl acrylate, sodium lauryl sulphate, synthetic polyacrylic ester compounded latex particle, other technology is with embodiment 1.(the results are shown in Table 2)
Table 2
*Linking agent add-on (internally olefin(e) acid butyl ester monomer weight ratio);
Comparative Examples 1
Methyl methacrylate (MMA) dropped into the polymerization that heats up in butyl polyacrylate (PBA) latex with sodium lauryl sulphate (KPS) when polyacrylic ester compounded latex shell was synthetic, and other technology is with implementing 1.(the results are shown in Table 3)
Comparative Examples 2
Polyacrylic ester compounded latex shell adds KPS when synthetic after PBA latex reaches polymerization temperature, then drip MMA continuously and carry out the polymerization of latex shell, and other technology is with embodiment 1.(the results are shown in Table 3)
Table 3
Comparative Examples 3
Need not 5% concentration NH after the polyacrylic ester compounded latex is synthetic
3.H
2The O titration is regulated the latex pH value to neutral, directly carries out graft polymerization with latex and vinylchlorid, and other technology is with embodiment 1.The granularity of copolymer resins is thicker as a result, and sticking still is heavier.
Comparative Examples 4
When polyacrylic ester latex and vinylchlorid graft copolymerization, polyacrylic ester latex and deionized water, dispersion agent, NaHCO
3At first one add in the still, adds vinyl chloride monomer after pressure testing vacuumizes again, adds initiator intensification polymerization, and other technology is with embodiment 1.(the results are shown in Table 4)
Comparative Examples 5
Add deionized water, dispersion agent, NaHCO earlier
3Go into still, add vinyl chloride monomer after pressure testing vacuumizes again, add initiator intensification polymerization, the adding polyacrylic ester latex was gone into still after vinylchlorid entered polymerization, and other technology is with embodiment 1.(the results are shown in Table 4)
Table 4
Claims (9)
1. the production method of a polyvinyl chloride special for high-impact-resisting building material product is characterized in that, comprises the steps:
(1) carry out emulsion polymerization with the raw material that comprises following component and mass fraction at least, obtain a kind of compounded latex of nucleocapsid structure, wherein, the nuclear part is a polyacrylic ester, and shell partly is a polyalkyl acrylate:
The composition weight umber
Deionized water 100
Acrylate 30-45
Alkyl acrylate 5.0-20
Emulsifying agent 0.10-2.00
Initiator 0.05-0.75
Dosage of crosslinking agent is the 0.5-2.0wt% of acrylate core monomer weight
Wherein linking agent is selected the toxilic acid polyene esters for use, and alkyl acrylate adopts the feeding mode of first swelling 0.5-1.0hr repolymerization;
(2) in above-mentioned compounded latex, add basic solution, regulate pH value to 6.0-9.0;
(3) to comprise the raw material graft polymerization of following component and mass fraction at least:
The composition weight umber
Vinyl chloride monomer 100
Deionized water 150-250
Step (2) compounded latex 15-30
Initiator 0.020-0.10
Dispersion agent 0.10-0.60
Reaction finishes, and promptly obtains vinyl chloride graft copolymer after centrifugal, the drying;
Compounded latex adds the mode of polymeric kettle for initially just to drop in the still with deionized water, dispersion agent, or adds in the still after monomer, water and dispersion agent adding stir again.
2. method according to claim 1 is characterized in that, acrylate is a butyl acrylate, and alkyl acrylate is a methyl methacrylate, and the weight ratio of acrylate and alkyl acrylate is 80～85: 15～20.
3. method according to claim 1 is characterized in that, the polymeric reaction temperature 70-90 of step (1) ℃, the reaction times is 6～9 hours; Temperature 40-60 ℃ of step (2), the time is 3.5～6.0 hours.
4. method according to claim 1 is characterized in that, acrylate adopts adding in batches or dropping mode continuously to add.
5. method according to claim 1 is characterized in that linking agent is selected diallyl maleate for use, and consumption is the 1.0wt% of acrylate core monomer weight.
6. according to each described method of claim 1～5, it is characterized in that the emulsifying agent of step (1) is selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or nonionogenic tenside.
7. method according to claim 6 is characterized in that, the initiator of step (1) is selected from thermolysis type or oxidation-reduction type, and thermolysis type initiator is selected peroxide or azo class.
8. method according to claim 7 is characterized in that, the dispersion agent of step (3) is selected from a kind of or its mixture in polyvinyl alcohol, methylcellulose gum, ethyl cellulose, Vltra tears, polyacrylic acid or the gelatin of partial alcoholysis.
9. method according to claim 7 is characterized in that, the initiator of step (3) is selected from organic peroxide evocating agent or azo-initiator.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4981907A (en) * | 1987-10-23 | 1991-01-01 | Hoechst Aktiengesellschaft | Process for the preparation of an acrylate-vinyl chloride graft polymer |
| CN1161345A (en) * | 1997-01-06 | 1997-10-08 | 化学工业部北京化工研究院 | Method for prodn. of high transparent and high impact resilience PVC |
| CN1510064A (en) * | 2002-12-25 | 2004-07-07 | 天津渤海化工有限责任公司天津化工厂 | Preparing method of high impact polyvinyl chloride resin with nuclear shell structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4981907A (en) * | 1987-10-23 | 1991-01-01 | Hoechst Aktiengesellschaft | Process for the preparation of an acrylate-vinyl chloride graft polymer |
| CN1161345A (en) * | 1997-01-06 | 1997-10-08 | 化学工业部北京化工研究院 | Method for prodn. of high transparent and high impact resilience PVC |
| CN1510064A (en) * | 2002-12-25 | 2004-07-07 | 天津渤海化工有限责任公司天津化工厂 | Preparing method of high impact polyvinyl chloride resin with nuclear shell structure |
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