CN101397356B - Method for preparing butadiene-styrene latex particle grafted polychloroethylene compound resin - Google Patents
Method for preparing butadiene-styrene latex particle grafted polychloroethylene compound resin Download PDFInfo
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- CN101397356B CN101397356B CN2008101531515A CN200810153151A CN101397356B CN 101397356 B CN101397356 B CN 101397356B CN 2008101531515 A CN2008101531515 A CN 2008101531515A CN 200810153151 A CN200810153151 A CN 200810153151A CN 101397356 B CN101397356 B CN 101397356B
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Abstract
A preparation method of styrene butadiene latex particle grafted polyvinyl chloride compound resin belongs to the polyvinyl chloride compound resin. The method includes the following steps: (1) cross-linked SBR compound particle latex is prepared; and (2) styrene butadiene latex particle grafted polyvinyl chloride compound resin is prepared; the direct grafting method of SBR compound particles and PVC is adopted to ensure that the grafted SBR/PVC compound resin takes the SBR compound particles as the kernel of an elastomer and the PVC as the shell of the compound resin particles. The styrene butadiene latex particle grafted polyvinyl chloride compound resin prepared by the method has high notch impact strength which is more than 8 times than the impact strength of the pure PVC; and the used styrene butadiene rubber has low price, thereby reducing the cost of the production of the impact resistant PVC .
Description
Technical field:
The present invention relates to polychloroethylene compound resin, the preparation method of specifically a kind of butadiene-styrene latex particle (SBR) grafted polychloroethylene compound resin.
Technical background:
Polyvinyl chloride (PVC) is a kind of general-purpose plastics of high comprehensive performance.After industrialization in 1936, its annual production increases day by day, and application in daily life is also increasingly extensive simultaneously.Up to the present, PVC has become second largest general synthetic plastics.The polyvinyl chloride resin good mechanical properties, synthesis technique is simple, usually by vinylchlorid (CH
2=CHCl) polymerization obtains.Owing in the polyvinyl chloride resin molecular chain a large amount of polar link C-Cl keys is arranged, exist big reactive force between the molecule, therefore polyvinyl chloride resin is harder, externally shows poor toughness, low, the poor heat resistance of notched Izod impact strength, has restricted its application in the higher field of performance requriements.
The toughening modifying of polyvinyl chloride (PVC) normally blend by PVC and plasticized modifier reaches, used properties-correcting agent generally is to have than the reduced TG invert point, with the rubber polymer that can form micro phase separation structure after PVC mixes, as ethylene-vinyl acetate copolymer (EVA), chlorinatedpolyethylene (CPE), nucleocapsid structure type acrylate copolymer (ACR), MBS (MBS) and acrylonitrile-butadiene-styrene copolymer (ABS) etc. disperse between inequality and disperse phase and matrix resin problems such as consistency difference but this method exists disperse phase in matrix resin.In recent years,, adopt graft copolymerization to obtain graft copolymerization toughening modifying PVC, become a kind of more effective approach of toughening modifying PVC in order to improve the consistency between plasticized modifier and the PVC.
The CN1743352 of the previous application of the present inventor discloses a kind of Polyurethane and Composite Normal Position Modify Pvc Resin and Preparation Method.What adopt is to be seed with urethane, makes the polyurethane-acrylate composite emulsion with nucleocapsid structure, in the presence of above-mentioned compounded latex, by emulsion (or suspension) graft polymerization vinyl chloride monomer, makes novel polychloroethylene compound resin then.But but adopt the shock strength of polychloroethylene compound resin of this method preparation not ideal enough, and production cost is higher.
The CN1418898 of the previous application of the present inventor discloses a kind of preparation method of high-impact polyacrylate composite particles grafting vinyl chloride emulsion resin, what adopt is to be main raw material with the acrylic ester monomer, by means such as seeded emulsion polymerization, organic agglomerant agglomeration and the addings of nano grade inorganic particle, make composite particles latex; In the presence of above-mentioned latex, warp and vinylchlorid grafting obtain the composite polrvinyl chloride emulsion resin.But because the price of acrylic ester monomer is higher, so it is higher to produce the price of this resin.
Summary of the invention:
It is low to the objective of the invention is to exist notched Izod impact strength at current PVC, the problem of poor toughness; The elastomerics particle disperses uneven problem during the blending modification method modification in matrix resin; Consistency difference problem between SBR and the PVC matrix, provide a kind of novel, production cost is low, the preparation method of the SBR/PVC compound resin of good impact resistance.
Technical scheme of the present invention is:
A kind of preparation method of butadiene-styrene latex particle grafted polyvinyl chloride (PVC) RESINS may further comprise the steps
(1) preparation (preparation of stratum nucleare) of crosslinked SBR composite particles emulsion
Add 100 parts of SBR composite particles quality of the emulsion umbers in reactor, add linking agent, its quality is 2～8% of the pure SBR composite particles quality that added; Solid content with deionized water adjusting SBR composite particles emulsion is 29-31% again; Stirred under the room temperature 2 hours, and be warming up to 75 ℃ then, insulation reaction 2 hours, cooling discharge promptly gets the SBR composite particles emulsion after crosslinked;
Described linking agent is Vinylstyrene (DVB) or Phthalic acid, diallyl ester (DCPA);
(2) preparation of butadiene-styrene latex particle grafted polychloroethylene compound resin (preparation of compound resin)
The constituent mass umber
Vinylchlorid 100
Deionized water 250～300
Emulsifying agent 1.0
Initiator 0.80
The crosslinked back SBR composite particles emulsion 10～60 that makes in the top step (1)
In autoclave by above-mentioned quality proportioning add ionized water, initiator, emulsifying agent and crosslinked after SBR composite particles emulsion, and be that the pH value of 5～10% sodium hydroxide solutions adjusting mixed reaction solution is 6.0～12.0 with mass percentage concentration; Inflated with nitrogen then, vacuumize, three times repeatedly, behind the excluding air, add vinyl chloride monomer and stir temperature reaction, the controlled polymerization temperature of reaction is at 45-60 ℃, when question response pressure was reduced to 0.1MPa, fast cooling to 30 ℃ vacuumized and removes unreacted gaseous vinyl chloride monomer, discharging, freezing breakdown of emulsion, vacuum-drying get butadiene-styrene latex particle grafted polyvinyl chloride resin powder foam;
The described emulsifying agent of step (2) is for using Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or sodium laurylsulfonate; Initiator is Potassium Persulphate, ammonium persulphate or Potassium Persulphate-S-WAT;
The constituent mass proportioning is polyhutadiene (PB) in the pure SBR composite particles of step (1): polystyrene (PS)=40～60:60～40.
The feed way of vinylchlorid is a continuous charging in the step (2);
Beneficial effect of the present invention is for adopting SBR composite particles and the direct grafted method of PVC, make SBR/PVC compound resin after the grafting by the SBR composite particles as elastomeric kernel, PVC is as the shell of composite resin particles; Wherein elastomeric kernel accounts for the 3-18% of composite resin particles gross weight, have following advantage: (1) direct graft polymerization has increased the interface binding power between SBR elastomerics and the matrix PVC, two alternate consistencies have been improved, improve the degree of scatter of rubber phase, improved elastomeric utilising efficiency greatly.(2) the SBR/PVC compound resin has very high notched Izod impact strength, reaches 36.03Kj/m as SBR/PVC composite resin material shock strength among the embodiment 14
2, be more than 8 times of pure PVC shock strength.(3) styrene-butadiene rubber(SBR) is cheap, and PVC has reduced cost for the production anti-impact.For the production of high-impact PVC provides a kind of novel method;
Description of drawings:
Fig. 1: the transmission electron microscope photo of the SBR/PVC composite particles that the embodiment of the invention 1 is prepared
Fig. 2: the transmission electron microscope photo of the SBR/PVC compound resin that the embodiment of the invention 1 is prepared
Fig. 3: pure emulsion PVC impacts the stereoscan photograph of batten section
Fig. 4: the scanning electron microscope of the impact section of the SBR/PVC composite resin material that the embodiment of the invention 1 is prepared
Embodiment:
Case study on implementation 1
(1) preparation (preparation of stratum nucleare) of crosslinked SBR composite particles emulsion: in the four-hole bottle that stirring, thermometer, reflux condensing tube, constant pressure funnel and drum nitrogen device are housed, add SBR emulsion 200g (quality proportioning polyhutadiene (PB) in the pure SBR component: polystyrene (PS)=50:50; ), emulsion solid content is 48%, the pure SBR composite particles quality that can calculate adding according to its solid content is 96 grams (solid content of SBR composite particles quality=SBR composite particles quality of the emulsion * emulsion, following steps and embodiment are together); Add linking agent DVB1.92g (quality of DVB be pure SBR composite particles quality 2%); Add deionized water 124.48g then, regulating emulsion solid content is 30%; Stirred 2 hours under the room temperature, be warming up to 75 ℃ then, insulation reaction promptly gets crosslinked SBR emulsion after 2 hours.
(2) preparation of butadiene-styrene latex particle grafted polychloroethylene compound resin (preparation of compound resin)
In the 2L stainless steel autoclave, add deionized water 662.5g, initiator potassium persulfate 2.12g, emulsifier sodium lauryl sulfate 2.65g by above-mentioned mass ratio, SBR composite particles emulsion 53.0g, and regulate the pH value of mixed reaction solution at 9.5-10.5 with mass ratio 5% sodium hydroxide solution.Inflated with nitrogen vacuumizes, three times repeatedly.Behind the excluding air, in still, feed vinyl chloride monomer 265g continuously, stir temperature reaction.The controlled polymerization temperature of reaction is in (50 ± 0.5) ℃, when question response pressure is reduced to 0.1MPa, fast cooling to 30 ℃, vacuumize (vacuum tightness is-0.08～-0.1MPa) removing unreacted vinyl chloride monomer, discharging, freezing breakdown of emulsion, vacuum-drying get New type of S BR/PVC compound resin powder.
(controlled temperature just can be realized in the middle polyreaction of step (2).The still internal pressure is raise gradually by vacuum state in the present embodiment, reach peak pressure 0.65～0.72MPa after, thereafter pressure along with the reaction carrying out progressively reduce.Following examples together)
The preparation of Mechanics Performance Testing sample: press table 1 prescription, after the resin that embodiment is made prepares with various auxiliary agent, be placed in the high-speed mixer mixing 10 minutes.Mixing on twin-roll machine mixed material then, 170～175 ℃ of control roller temperature, the thin-pass number of times is 12 times, the about 0.8mm of slice thickness.With going out sheet material on request thickness overlay in the mould, preheating is 10 minutes in 175 ℃ of following hydropress, is forced into the 5MPa pressurize 4 minutes, 10MPa pressurize 4 minutes, the typing of then colding pressing under chilling press is impacted and tensile bars usefulness for tailoring.
Table 1 vinylchlorid graft copolymerization resin treatment test raw material prescription
Shock strength test: above-mentioned sheet coupon is cut into the notch shock batten by the GB/T1043-93 standard with omnipotent sampling machine, at least after placing 24 hours, carry out shock test on the XCJ-40Charpy charpy impact test machine that trier factory in Chengde produces, probe temperature is 25 ℃.
The tensile property test: institute's panel is cut into the dumbbell shape tensile bars by the GB/T1040-92 standard, tests its tensile strength with RGT-10A type microcomputer control electronics universal testing machine down at 23 ℃, draw speed is 20mm/min, and probe temperature is 25 ℃.
According to the test method of GB-1633-79 softening temperature (dimension card), measure thermoplastics in liquid heat-transfer medium, at certain load, under 50 ℃ of intensification conditions, sample is by 1 millimeter
2Temperature when indentor point is pressed into 1 millimeter.Determining instrument is the thermal distortion of XWB-300F type, vicat softening point temperature determinator.
Transmission electron microscope (TEM) is analyzed: at first SBR/PVC composite particles emulsion is diluted with deionized water, used ultrasonic oscillation again 2 minutes, make emulsion particle obtain disperseing.Dry on copper mesh with the clean dropper emulsion droplets that takes a morsel then, the SBR composite particles in the emulsion particle is dyeed TECNAIG mutually with phospho-wolframic acid
220 type transmission electron microscope observing SBR/PVC composite particles forms.
With SBR/PVC matrix material batten ultrathin section(ing) under liquid nitrogen freezing, with perosmic anhydride SBR composite particles in the composite resin material is dyeed mutually, use TECNAIG
2The morphological structure of disperse phase in the 20 type transmission electron microscope observing materials.
Scanning electron microscope (SEM) is analyzed: will impact batten section end saw down, make the about 3～4mm of section end length, and under vacuum condition that sample section is gold-plated, with the shape characteristic of Philips XL30 type sem observation fracture surface.
Fig. 1 is the transmission electron microscope photo of the prepared SBR/PVC composite particles of the embodiment of the invention 1.As can be seen from the figure SBR/PVC composite emulsion particle has tangible nucleocapsid structure, and wherein the dark part of internal layer is chromatophilous SBR particle, and skin is divided into achromatic polyvinyl chloride than superficial part.
The transmission electron microscope photo of the SBR/PVC compound resin that Fig. 2 embodiment of the invention 1 is prepared, the disperse phase of black is the SBR particle, PVC is easy coloring not, presents external phase.The morphological structure of matrix material shows as " island " type two phase structure of micron-scale phase separation as can be seen from the figure, and quite is evenly dispersed in the PVC matrix.
The SBR/PVC compound resin that Fig. 4 makes for the embodiment of the invention 1 impacts the stereoscan photograph of batten section, the pure emulsion PVC of comparison diagram 3 impact the stereoscan photograph of batten sections, and the section of Fig. 4 matrix surrender reticulated structure that presents the gauffer injustice shows as the feature of tangible ductile rupture as can be seen.
Case study on implementation 2-5
The preparation (preparation of stratum nucleare) (1) of crosslinked SBR composite particles emulsion is identical in case study on implementation 2-5 and the case study on implementation 1, the quality that changes the middle SBR composite particles emulsion of preparation (preparation of compound resin) of (2) butadiene-styrene latex particle grafted polychloroethylene compound resin in the case study on implementation 1 is respectively 26.5g, 79.5g, 106g, 159g, and all the other operations are identical with case study on implementation 1.
Case study on implementation 6-8
Case study on implementation 6-8 is identical with the preparation (preparation of compound resin) of (2) butadiene-styrene latex particle grafted polychloroethylene compound resin in the case study on implementation 1, the quality that changes the middle linking agent DVB of preparation (preparation of stratum nucleare) of (1) crosslinked SBR composite particles emulsion is respectively 4% of pure SBR composite particles quality, 6%, 8%, and the deionized water quality that regulate to add makes SBR composite particles emulsion solid content after crosslinked 30%.All the other operations are identical with case study on implementation 1.
The preparation embodiment of table 1 stratum nucleare
Case study on implementation 9
Case study on implementation 9 is identical with the preparation (preparation of compound resin) of (2) butadiene-styrene latex particle grafted polychloroethylene compound resin in the case study on implementation 1, the linking agent DVB that changes in the preparation (preparation of stratum nucleare) of (1) crosslinked SBR composite particles emulsion is DCPA, and all the other operations are identical with case study on implementation 1.
Case study on implementation 10-12
Case study on implementation 10-12 for a change among the case study on implementation 6-8 linking agent DVB in the preparation (preparation of stratum nucleare) of (1) crosslinked SBR composite particles emulsion be DCPA, the preparation (preparation of compound resin) of all the other operations and (2) butadiene-styrene latex particle grafted polychloroethylene compound resin is identical with case study on implementation 6-8.
The preparation embodiment of table 2 stratum nucleare
Case study on implementation 13
The preparation of (2) butadiene-styrene latex particle grafted polychloroethylene compound resin (preparation of compound resin) is identical with case study on implementation 1 in the case study on implementation 13, changes SBR emulsion (the pure SBR composite particles constituent mass proportioning polyhutadiene (PB): polystyrene (PS)=50:50 in the preparation (preparation of stratum nucleare) of (1) crosslinked SBR composite particles emulsion; Solid content 48%) is SBR emulsion (pure SBR composite particles constituent mass proportioning polyhutadiene (PB): polystyrene (PS)=40:60; Solid content 48%), all the other operations are identical with case study on implementation 1.
Case study on implementation 14
Case study on implementation 14 is identical with the preparation (preparation of compound resin) of (2) butadiene-styrene latex particle grafted polychloroethylene compound resin in the case study on implementation 1, changes SBR emulsion (the pure SBR composite particles constituent mass proportioning polyhutadiene (PB): polystyrene (PS)=50:50 in the preparation (preparation of stratum nucleare) of (1) crosslinked SBR composite particles emulsion; Solid content 48%) is SBR emulsion (pure SBR composite particles constituent mass proportioning polyhutadiene (PB): polystyrene (PS)=60:40; Solid content 48%), all the other operations are identical with case study on implementation 1.
Case study on implementation 15-16
The preparation (preparation of stratum nucleare) of (1) crosslinked SBR composite particles emulsion is identical in case study on implementation 15-16 and the case study on implementation 1, change polymerization temperature (50 ± 0.5) in the preparation (preparation of compound resin) of (2) butadiene-styrene latex particle grafted polychloroethylene compound resin and ℃ be respectively (45 ± 0.5) ℃, (60 ± 0.5) ℃, all the other operations are identical with case study on implementation 1.
Synthetic SBR/PVC composite resin material performance table look-up in table 3 example
By the listed example synthetic of above-mentioned table 3 SBR/PVC composite resin material performance as can be seen, institute's synthetic SBR/PVC composite resin material has impelling strength preferably, and wherein SBR/PVC composite resin material shock strength reaches 36.03Kj/m among the embodiment 14
2, be more than 8 times of pure PVC shock strength, and when shock strength improved, the tensile strength decline scope not too.
Claims (1)
1. the preparation method of a butadiene-styrene latex particle grafted polyvinyl chloride (PVC) RESINS is characterized by and may further comprise the steps
(1) preparation of stratum nucleare: the preparation of crosslinked SBR composite particles emulsion
Add 100 parts of SBR composite particles quality of the emulsion umbers in reactor, add linking agent, its quality is 2～8% of the pure SBR composite particles quality that added; Solid content with deionized water adjusting SBR composite particles emulsion is 29-31% again; Stirred under the room temperature 2 hours, and be warming up to 75 ℃ then, insulation reaction 2 hours, cooling discharge promptly gets the SBR composite particles emulsion after crosslinked;
Described linking agent is Vinylstyrene DVB or Phthalic acid, diallyl ester;
(2) preparation of compound resin: the preparation of butadiene-styrene latex particle grafted polychloroethylene compound resin
The constituent mass umber
Vinylchlorid 100
Deionized water 250～300
Emulsifying agent 1.0
Initiator 0.80
The crosslinked back SBR composite particles emulsion 10～60 that makes in the top step (1)
In autoclave by above-mentioned quality proportioning add deionized water, initiator, emulsifying agent and crosslinked after SBR composite particles emulsion, and be that the pH value of 5～10% sodium hydroxide solutions adjusting mixed reaction solution is at 9.5-10.5 with mass percentage concentration; Inflated with nitrogen then, vacuumize, three times repeatedly, behind the excluding air, add vinyl chloride monomer and stir temperature reaction, the controlled polymerization temperature of reaction is at 45-60 ℃, when question response pressure was reduced to 0.1MPa, fast cooling to 30 ℃ vacuumized and removes unreacted gaseous vinyl chloride monomer, discharging, freezing breakdown of emulsion, vacuum-drying get butadiene-styrene latex particle grafted polyvinyl chloride resin powder end;
The described emulsifying agent of step (2) is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or sodium laurylsulfonate; Initiator is Potassium Persulphate, ammonium persulphate or Potassium Persulphate-S-WAT;
Wherein the constituent mass ratio is polyhutadiene PB in the pure SBR composite particles of step (1): polystyrene PS=40～60: 60～40;
The feed way of vinylchlorid is a continuous charging in the described step (2).
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| CN2008101531515A CN101397356B (en) | 2008-11-19 | 2008-11-19 | Method for preparing butadiene-styrene latex particle grafted polychloroethylene compound resin |
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| CN101397356B true CN101397356B (en) | 2010-08-18 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2945539B1 (en) * | 2009-05-15 | 2012-05-18 | Arkema France | PROCESS FOR PREPARING SUSPENDED PVC GRAFT ON ELASTOMER. |
| CN102174150B (en) * | 2011-02-11 | 2012-05-23 | 福建师范大学 | Grafting modification method for elastomer resin fusant |
| CN102952301B (en) * | 2011-08-19 | 2014-10-15 | 中国石油天然气股份有限公司 | Preparation method of oil resistant enhanced styrene-butadiene rubber polymer particles |
| CN111450772A (en) * | 2020-04-27 | 2020-07-28 | 南京泰佳化工有限公司 | Non-layering liquid sodium alkyl benzene sulfonate and preparation method thereof |
| CN112358694A (en) * | 2020-09-30 | 2021-02-12 | 杭州富通电线电缆有限公司 | Polyvinyl chloride cable material and preparation method thereof |
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Assignee: Anqing Linghu Paint Co.,Ltd. Assignor: Hebei University of Technology Contract record no.: 2011340000080 Denomination of invention: Method for preparing butadiene-styrene latex particle grafted polychloroethylene compound resin Granted publication date: 20100818 License type: Exclusive License Open date: 20090401 Record date: 20110701 |
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