CN100368444C - Process for preparing vinyl chloride/nano calcium carbonate in-situ polymerization resin - Google Patents
Process for preparing vinyl chloride/nano calcium carbonate in-situ polymerization resin Download PDFInfo
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- CN100368444C CN100368444C CNB2004100847762A CN200410084776A CN100368444C CN 100368444 C CN100368444 C CN 100368444C CN B2004100847762 A CNB2004100847762 A CN B2004100847762A CN 200410084776 A CN200410084776 A CN 200410084776A CN 100368444 C CN100368444 C CN 100368444C
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 71
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 56
- 239000011347 resin Substances 0.000 title claims abstract description 41
- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 38
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims description 47
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 239000006185 dispersion Substances 0.000 claims description 31
- 239000000945 filler Substances 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 5
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical group OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 5
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 238000007796 conventional method Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 63
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 58
- 239000000463 material Substances 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000010558 suspension polymerization method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000006136 alcoholysis reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- -1 alkyl alcohol sulfate class Chemical class 0.000 description 7
- 238000005502 peroxidation Methods 0.000 description 7
- 238000010557 suspension polymerization reaction Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HQDAJGNZGNZGCO-UHFFFAOYSA-N (propan-2-ylideneamino)urea Chemical compound CC(C)=NNC(N)=O HQDAJGNZGNZGCO-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- WLUUTGIJNRNHRF-UHFFFAOYSA-N tert-butyl heptanoate Chemical compound CCCCCCC(=O)OC(C)(C)C WLUUTGIJNRNHRF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Polymerisation Methods In General (AREA)
Abstract
The present invention discloses a method for preparing vinyl chloride/nano calcium carbonate in-situ polymerization resin. When the present invention adopts a suspension polymerization method for preparing polyvinyl chloride resin, the filling material of nano calcium carbonate is uniformly dispersed in vinyl chloride monomers in advance; as a result, the surfaces of particles of nano filling material chemically react with chloroethylene, etc. or physically adsorb the chloroethylene, etc.; consequently, the physical properties and the mechanical properties of products of polyvinyl chloride plastics are greatly improved.
Description
Technical field
The present invention relates to a kind of polyvinyl chloride (PVC) RESINS, particularly a kind of preparation method of vinylchlorid/nano calcium carbonate in-situ polymerization resin.
Background technology
Polyvinyl chloride (PVC) RESINS is called for short polyvinyl chloride resin.Vinylchlorid/nano calcium carbonate in-situ polymerization resin, be that nano level inorganic rigid particle calcium carbonate particles is disperseed to be filled in the polyvinyl chloride resin base with the method for in-situ polymerization, just " naturally ", " in situ " participate in its reaction process even nano-calcium carbonate is in the polymerization of vinyl choride monomer stage, thereby better be implemented in dispersion and filling in the polymeric matrix, effectively avoid self reuniting of nanoparticle, comprehensively improve the performance of resin, especially improve the erosion-resisting characteristics of PVC.
Because nano grain surface has chemical bond to be connected with the polyvinyl chloride matrix, and it is more much more difficult than the Van der Waals force that overcomes between polyvinyl chloride to make chemical bond rupture, therefore under external force, nano particle and polyvinyl chloride matrix are difficult to peel off, and cause the mechanical property of the polyvinyl chloride (PVC) RESINS of nanometer in-situ polymerization obviously to be better than the blend filled composite materials;
In addition, the part nano particle since in the particle polyreaction heat built-up and monomer in nano pore, fill the disintegration that STRESS VARIATION caused that polymerization causes, also be one of reason of significantly improving of the mechanical property of materials.Discrete particles diameter after the disintegration is 5～10nm, and the specific surface that makes nano material has been realized the inaccessiable nano level small size dispersion of previous compounding technology institute up to more than the 100m2/g.Above reason makes the mechanical property of the polyvinyl chloride (PVC) RESINS that the nanometer in-situ polymerization makes have increased significantly, the vinylchlorid/nanometer CaCO in chemical plant, Taiyuan
3The prepared polyvinyl chloride resin of in-situ polymerization technology is brought up to more than 4 times than the shock strength of common PVC resin, and tensile strength also improves a lot.
CaCO
3The performance impact of filled PVC depends primarily on three aspect factor: (1) CaCO
3The median size of basic crystal grain, CaCO
3The particle diameter of particle is more little, and toughening effect is obvious more; (2) CaCO
3Apparent particle diameter; (3) CaCO
3The surfactivity of molecule.Dissimilar CaCO
3Filling effect to polymkeric substance is different, because when weighting agent only combines with very weak physical force with resin, mainly show as incremental contribution, little to the mechanical property influence that improves system, CaCO only takes measures to increase
3And when avidity between the macromolecule surface or chemical force, just may get a desired effect.
In the suspension polymerization of VC process, be added into nanometer CaCO
3After, the relative molecular mass of resin and dispersion index are all increased to some extent.The whiteness of resin and plasticizer absorption increase with the increase of the addition of nano material.Mainly be because nanometer CaCO
3Absorb the HCl that the low-molecular material decomposition is emitted in polymkeric substance aftertreatment and the drying process, stoped its further decomposition; In addition, a large amount of suspended double bond that the nano grain surface coordination does not cause have entirely replaced the unstable chlorine atom on the macromolecular chain, make PVC molecular chain stabilization.
The apparent density of the polyvinyl chloride resin of nanometer in-situ polymerization gained and oil absorbency are not the index of two mutual contradictions, and they have obtained synchronous raising, mainly are because nanometer CaCO
3Be adsorbed on the monomer droplet surface as inorganic dispersant, played the mechanically stable effect, learn by electron microscope observation, product is in the majority with unicellular particle, has verified this viewpoint; Nanometer CaCO
3Entered PVC primary particle inside in position in the polymerization process, also made the weightening finish of PVC powder granule.Certainly, different polymeric kettle shape and stirring systems still have influence to the performance of resin.Comprehensive above performance, this product is very favourable as the chemical building material PP Pipe Compound.But present technology is usually at nanometer CaCO
3Surface treatment process in introduce some surface treatment agent.Thereby introduced other chemical ingredients, not only increased production cost, also inevitably will affect simultaneously, as causing polymerization time to prolong or not step-down, resin size distribution broaden, fine particle increases or produce phenomenon such as oversize particle to PVC in-situ suspension polymerization system.
The technical issues that need to address of the present invention provide the suspension in-situ polymerization of a kind of vinylchlorid and nano-calcium carbonate, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
The present invention is adopting suspension polymerization to prepare in the process of polyvinyl chloride (PVC) RESINS, be evenly dispersed in the nano-calcium carbonate filler in the vinyl chloride monomer in advance, make the surface of Nano filling particle and vinylchlorid etc. that chemical reaction or physical adsorption take place, thereby increase substantially the physical and mechanical properties of polyvinyl chloride plastic material products.
Method of the present invention comprises the steps:
The polymer raw that will comprise vinyl chloride monomer, initiator, dispersion agent, water, pH regulator agent and nano-calcium carbonate filler adopts conventional method to carry out polyreaction, reaction times is 4.0～7.0 hours, temperature of reaction is 30～70 ℃, said initiator, dispersion agent, water, pH regulator agent and consumption thereof are technology well known in the art, as " polyvinyl chloride technique " disclosed technology.It is characterized in that said nano-calcium carbonate filler is surface treated, its preparation method is as follows:
Nano-calcium carbonate emulsion, PVC seed emulsion are mixed homogenizing add dispersion agent again, under certain reaction conditions, carry out homogenizing then, promptly obtained surface-treated nano-calcium carbonate filler;
The temperature that nano-calcium carbonate emulsion, PVC seed emulsion are mixed homogenizing is 10～60 ℃, and homogenization pressures is 0.05～0.5Mpa, and the time is 0.1～1.0 hour;
The weight solid content of said nano-calcium carbonate emulsion is 5～15%, and the particle diameter of lime carbonate wherein is 10～100nm;
The weight solid content of PVC seed emulsion is 15～50%;
Said dispersion agent is selected from hydroxypropyl methyl cellulose ether, and as E50 or F50, polyvinyl alcohol, as KH20 or LM22, dispersant dosage is 1～20% of a nano-calcium carbonate emulsion weight;
The contriver finds that the usage quantity of handling the PVC seed emulsion of nano-calcium carbonate will be very effective in a comparatively narrow scope, preferred weight consumption is:
The dry weight of PVC seed emulsion (being PVC seed emulsion weight * emulsion solid content): in the scope of the dry weight of nano-calcium carbonate (nano-calcium carbonate slurries * slurry solid content)=1～1: 30, its optimum range is 1: 5～15;
The performance of said PVC seed emulsion is very crucial to the surface treatment effect of calcium carbonate particles, be used for the synthetic of nano-calcium carbonate surface-treated PVC seed emulsion, need to adjust its emulsifying agent consumption, feed way, polymerization time etc., with the solid content of control emulsion, the indexs such as size of latex particle, to meet the needed effect of surface treatment better.
The PVC seed emulsion is to comprise the preparation of following component and raw materials in weight content:
100 parts in vinylchlorid
0.5～5 part of emulsifying agent
0.5～5 part of initiator
0.01～0.2 part of pH regulator agent
115～125 parts in water
Polymerization temperature is 40～60 ℃, and polymerization time is 4～8 hours;
Said emulsifying agent is selected from one or more in alkyl alcohol sulfate class, alkyl alcohol Sulfonates or the alkyl naphthalene sulfonic acid salt, and the feed way of emulsifying agent can be directly once to add or add in batches;
The pH regulator agent is selected from ammoniacal liquor, NaHCO
3Or NH
4HCO
3In a kind of, be used for regulating polymerization system pH value, the resin particle of improvement form is also arranged, improve effects such as apparent density;
Gained PVC seed emulsion median size is 50～100nm, preferably its particle size range is controlled at 50～80nm, the surface treatment of the nanoparticle of being more convenient for.
Said initiator is selected from ammonium persulphate, Potassium Persulphate or organo-peroxide, initiator can be directly once to add or add in batches, the said organo-peroxide that draws is selected from peroxidation neodecanoic acid isopropyl benzene ester (Tx99), peroxidation neodecanoic acid-2,4,4-trimethylammonium pentyl ester (Tx423), peroxy dicarbonate is two-(2-ethylhexyl) (EHP), the special butyl ester (Tx23) of peroxidation neodecanoic acid, the new enanthic acid tert-butyl ester of peroxidation (Tx257), the special pentyl ester (Tx125) of peroxidation trimethylacetic acid, peroxide tert pivalate ester (Tx25), peroxidation two-(3,5, the 5-trimethyl acetyl) (Tx36), in the dilauroyl peroxide (LPO) one or more.
Said dispersion agent does not have very big influence to polymerization, can adopt comparatively popular of the present world, as the binary polyvinyl alcohol, or the mixture of polyvinyl alcohol and cellulose ethers (as hydroxypropyl methyl cellulose ether etc.), preferred employing alcoholysis degree is 45～80mol%, the polymerization degree is 250～2000 PVA dispersion agent, as trade names is KH20, the trade names that U.S. DOW chemical company produces are the Vltra tears dispersion agent of E50, the trade mark that Britain Harco company produces is the dispersion agent of B72, has stronger dispersive ability, be applied to PVC suspension polymerization, can produce and keep than high apparent density, the polyvinyl chloride resin that has high porosity simultaneously, thereby make the particle form of resin regular, VC takes off absorption can be good, fusion time is short, narrower particle size distribution, and the bubble can reduce polymerization the time is smeared.With the stronger compound use of KH20PVA dispersion agent of guarantor's glue ability, help improving the over-all properties of polyvinyl chloride resin; It is higher that L-9-78 is that Japanese Kuraray company develops " cloud point ", the PVA dispersion agent of alcoholysis degree 76.5～79.0mol%, help improving the apparent density of resin, be applicable to that also hot water is reinforced, LM22 (the polymerization degree 250 of Japan Kuraray company, LW300 (the polymerization degree 250 of alcoholysis degree 47.0～53.0mol%) and Japanese synthetic chemistry company, alcoholysis degree 53.0～60.0mol%) is a new type water-solubility low alcoholysis level PVA dispersion agent, with height, the middle compound use of alcoholysis degree PVA can further make the resin particle form regular, improve porosity, plasticizing capacity and VC take off the absorption energy.
The weight percent content of surface treated nano-calcium carbonate filler is 5～50% in vinylchlorid/nano calcium carbonate in-situ polymerization resin.
Structure through PVC seed emulsion surface-treated nano-calcium carbonate is made up of three basic parts, in basic particulate unit, filler is a lime carbonate, mainly play density, improve rigidity, effect such as reduce cost, be wrapped in the outer coupling layer of lime carbonate, mainly be made up of the PVC that filler nuclear and superpolymer is played simultaneously chemical and physical action, it can improve the bonding force between filler and superpolymer.Dispersion layer mainly is to be made of low-molecular weight polymer or lipid acid and its esters.The pearl filler of handling through PVC, use the dispersion agent surface treatment again, can improve the dispersiveness of pearl filler greatly, to avoid the caking of reuniting, thereby can obtain the higher filled articles of visual appearance, this point is even more important in plastics are filling-modified.
The PVC seed emulsion can coat last layer PVC polymkeric substance with after tiny nano-calcium carbonate slurries mix homogenizing on the nano-calcium carbonate surface, the microemulsified process promptly take place.One deck PVC polymkeric substance on nano-calcium carbonate particles surface can promptly be had good affinity and consistency with the VC monomer by VC monomer institute swelling, can reach the desired surface treatment effect of in-situ polymerization.Another advantage of using the PVC seed emulsion is not select to introduce other chemical reagent composition in whole PVC in-situ polymerization system because of the kind of surface treatment agent.Because the composition in the PVC seed emulsion is deionized water, PVC, small amounts of emulsifiers, and the initiator of trace (content＜＜PPM level), wherein emulsifying agent plays important effect to the microemulsified process of nano-calcium carbonate, PVC suspension polymerization also there is certain dissemination, deionized water and PVC then were exactly the essential substance in the PVC suspension polymerization originally, and the used initiator of letex polymerization can be ignored its influence owing to content is extremely low.Therefore, use the PVC seed emulsion introducing of surface treatment agent can be reduced to minimum level to the influence that PVC in-situ suspension polymerization system causes as the surface treatment agent of nano-calcium carbonate.
Adopt the vinylchlorid/nano calcium carbonate in-situ polymerization resin of method preparation of the present invention, production cost reduces by 10% than conventional method, and its mechanical property is good, to the product mechanical detection that is obtained, the result shows, meets or surpass relevant department's set quota fully.
Embodiment
Embodiment 1
(1) preparation of PVC seed emulsion:
Water with 100 kilograms of vinylchlorid, 1.5 kilograms of dodecyls alcohol sodium sulfate, 0.5 kilogram of initiator ammonium persulfate, 0.2 kilogram of pH regulator agent ammoniacal liquor and 120 kg, 50 ℃ of polyreactions 4 hours, promptly obtain the PVC seed emulsion, the weight solid content is 30%, and gained PVC seed emulsion median size is 70nm;
(2) preparation of surface treated nano-calcium carbonate filler:
With 20 kilograms of solid contents is that 35% nano-calcium carbonate emulsion, 5 kilograms of above-mentioned PVC seed emulsion are mixed homogenizing and added 5 kilograms of dispersion agents again (trade names are KH20, alcoholysis degree is 80mol%), homogenizing is 0.5 hour under 20 ℃ of temperature, promptly obtains surface-treated nano-calcium carbonate filler;
(3) preparation of target product:
57 ℃ of polymerization temperatures, discharging behind the pressure drop 0.15MPa.
100 kilograms of vinyl chloride monomers, dispersion agent (KH20/E50/LM22) consumption is 0.25 kilogram, the initiator peroxy dicarbonate is two-(2-ethylhexyl) (EHP) 0.1 kilogram, and 0.05 kilogram of pH regulator agent (NaOH), 0.009 kilogram of terminator (acetone semicarbazone thiocarbamide); 10 kilograms of the nano-calcium carbonates of step (2), 240 kilograms of de-salted waters.
The nano-calcium carbonate, the de-salted water that in the 10L polymermaking autoclave, add initiator, dispersion agent, step (2), N
2Be pressed into vinyl chloride monomer after the displacement, heat up, carry out polyreaction, after 1.5 hours, add pH regulator agent aqueous solution 1.5hr with volume pump stream, behind the reaction pressure decline 0.15MPa, stopped reaction, drying is carried out in discharging then.Polymerization time is 4.75hr, and the pressure drop time is 0.72hr, and the resin mean polymerisation degree is 1025, apparent density 0.44g/ml, plasticizer absorption rate 26.0g/100g, sieving rate (65 orders/250 orders, %) be 99.2/2.5, after resin treatment became goods, shock strength was 18.73KJ/m3.
The material breach erosion-resisting characteristics of the said products adopts the GB/T1043-93 standard to detect.
Embodiment 2
Adopt the method identical with embodiment 1, difference is:
The preparation method of surface treated nano-calcium carbonate filler is as follows:
(1) preparation of PVC seed emulsion:
Water with 100 kilograms of vinylchlorid, 1.5 kilograms of dodecyls alcohol sulfonate sodium, 0.5 kilogram of initiator ammonium persulfate, 0.2 kilogram of pH regulator agent ammoniacal liquor and 120 kg, 50 ℃ of polyreactions 4 hours, promptly obtain the PVC seed emulsion, the weight solid content is 30%, and gained PVC seed emulsion median size is 60nm;
(2) preparation of surface treated nano-calcium carbonate filler:
With 20 kilograms of solid contents is that 35% nano-calcium carbonate emulsion, 5 kilograms of above-mentioned PVC seed emulsion are mixed homogenizing and added 5 kilograms of dispersion agents again (trade names are KH20, alcoholysis degree is 80mol%), homogenizing is 0.5 hour under 20 ℃ of temperature, promptly obtains surface-treated nano-calcium carbonate filler;
(3) preparation of target product:
57 ℃ of polymerization temperatures, discharging behind the pressure drop 0.15MPa.
100 kilograms of vinyl chloride monomers, dispersion agent (KH20/E50/LM22) consumption is 0.25 kilogram, special butyl ester (Tx23) 0.1 kilogram of initiator peroxidation neodecanoic acid, 0.05 kilogram of pH regulator agent (NaOH), 0.009 kilogram of terminator (acetone semicarbazone thiocarbamide); 20 kilograms of the nano-calcium carbonates of step (2), 240 kilograms of de-salted waters.
Resin colloidal sol mean polymerisation degree is 1020, apparent density 0.41g/ml, and plasticizer absorption rate 29.0g/100g, (65 orders/250 orders are 99.5/2.1 %) to sieving rate, and after resin treatment became goods, shock strength was 27.73KJ/m3.
Embodiment 3
Adopt the method identical with embodiment 1, difference is:
Being prepared as follows of PVC seed emulsion:
Water with 100 kilograms of vinylchlorid, 1.5 kilograms of sodium lauryl sulphate (adding), 0.5 kilogram of initiator ammonium persulfate, 0.25 kilogram of dispersion agent hydroxypropyl methyl cellulose ether (trade names are E50), 0.2 kilogram of pH regulator agent ammoniacal liquor and 120 kg in batches, 50 ℃ of polyreactions 4 hours, promptly obtain the PVC seed emulsion, the weight solid content is 20%, and gained PVC seed emulsion median size is 55nm;
(2) preparation of surface treated nano-calcium carbonate filler:
With 20 kilograms of solid contents is that 35% nano-calcium carbonate emulsion, 5 kilograms of above-mentioned PVC seed emulsion are mixed homogenizing and added 5 kilograms of dispersion agents again (trade names are LM22, alcoholysis degree is 45mol%), homogenizing is 0.5 hour under 50 ℃ of temperature, promptly obtains surface-treated nano-calcium carbonate filler;
(3) preparation of target product:
57 ℃ of polymerization temperatures, discharging behind the pressure drop 0.15MPa.
100 kilograms of vinyl chloride monomers, dispersion agent (KH20/E50/LM22) consumption is 0.25 kilogram, the initiator peroxy dicarbonate is two-(2-ethylhexyl) (EHP) 0.1 kilogram, and 0.05 kilogram of pH regulator agent (NaOH), 0.009 kilogram of terminator (acetone semicarbazone thiocarbamide); 20 kilograms of the nano-calcium carbonates of step (2), 240 kilograms of de-salted waters.
Resin colloidal sol mean polymerisation degree is 995, apparent density 0.43g/ml, and plasticizer absorption rate 23.0g/100g, (65 orders/250 orders are 98.0/8.9 %) to sieving rate, and after resin treatment became goods, shock strength was 27.45KJ/m3.
Comparative Examples 1
57 ℃ of polymerization temperatures, discharging behind the pressure drop 0.15Mpa;
100 kilograms of vinyl chloride monomers, dispersion agent (KH20/E50/LM22) consumption is 0.25 kilogram, 0.1 kilogram of initiator (EHP), 0.05 kilogram of pH regulator agent (NaOH), 0.009 kilogram of terminator (acetone semicarbazone thiocarbamide), 240 kilograms of de-salted waters.
In the 10L polymermaking autoclave, add initiator, dispersion agent, de-salted water, N
2Be pressed into vinyl chloride monomer after the gas displacement, heat up, carry out polyreaction, after 1.5 hours, add pH regulator agent aqueous solution 1.5hr with volume pump stream, behind the reaction pressure decline 0.15MPa, stopped reaction, drying is carried out in discharging then.Polymerization time is 5.52hr, and the pressure drop time is 0.80hr, and resin colloidal sol mean polymerisation degree is 1020, apparent density 0.45g/ml, plasticizer absorption rate 24.7g/100g, sieving rate (65 orders/250 orders, %) be 99.5/1.7, after resin treatment became goods, shock strength was 8.11KJ/m3.
By above 3 embodiment and Comparative Examples 1 more as can be seen, in polymerization reaction system, add nano-calcium carbonate after, resin resistance to impact shock after processing obviously improves.
Claims (6)
1. the preparation method of a vinylchlorid/nano calcium carbonate in-situ polymerization resin comprises the steps:
The polymer raw that will comprise vinyl chloride monomer, initiator, dispersion agent, water, pH regulator agent and nano-calcium carbonate filler adopts conventional method to carry out polyreaction, initiator be peroxy dicarbonate two-(2-ethylhexyl), dispersion agent is KH20/E50/LM22, the PH conditioning agent is a sodium hydroxide, it is characterized in that, said nano-calcium carbonate filler is surface treated, and the preparation method is as follows:
Nano-calcium carbonate emulsion, PVC seed emulsion are mixed homogenizing add dispersion agent again, homogenizing promptly obtained surface-treated nano-calcium carbonate filler then;
Said dispersion agent is selected from hydroxypropyl methyl cellulose ether or polyvinyl alcohol, and dispersant dosage is 1～20% of a nano-calcium carbonate emulsion weight;
The dry weight of PVC seed emulsion: the dry weight of nano-calcium carbonate=1～1: 30;
The PVC seed emulsion is to comprise the preparation of following component and raw materials in weight content:
100 parts in vinylchlorid
0.5～5 part of emulsifying agent
0.5～5 part of initiator
0.01～0.2 part of pH regulator agent
115～125 parts in water
Said emulsifying agent is selected from one or more in alkyl alcohol sulfate, alkyl alcohol sulfonate or the sulfonated alkyl naphathalene;
PVC seed emulsion median size is 50～100nm;
Said initiator is selected from ammonium persulphate, Potassium Persulphate or organo-peroxide.
2. method according to claim 1 is characterized in that, the temperature that nano-calcium carbonate emulsion, PVC seed emulsion are mixed homogenizing is 10～60 ℃, and homogenization pressures is 0.05～0.5Mpa, and the time is 0.1～1.0 hour.
3. method according to claim 1 is characterized in that, the weight solid content of said nano-calcium carbonate emulsion is 5～15%, and the particle diameter of lime carbonate wherein is 10～100nm; The weight solid content of PVC seed emulsion is 15～50%.
4. method according to claim 1 is characterized in that, the dispersion agent when preparing surface treated nano-calcium carbonate filler is selected from hydroxypropyl methyl cellulose ether or polyvinyl alcohol, and dispersant dosage is 1～20% of a nano-calcium carbonate emulsion weight.
5. method according to claim 1 is characterized in that the pH regulator agent is selected from ammoniacal liquor, NaHCO
3Or NH
4HCO
3In a kind of.
6. according to each described method of claim 1～5, it is characterized in that the weight ratio of surface treated nano-calcium carbonate filler is 2～50 in vinylchlorid/nano calcium carbonate in-situ polymerization resin.
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Cited By (3)
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| WO2020091427A1 (en) * | 2018-11-02 | 2020-05-07 | 주식회사 엘지화학 | Method for preparing vinyl chloride-based polymer |
| WO2020091429A1 (en) * | 2018-11-02 | 2020-05-07 | 주식회사 엘지화학 | Composition for preparing vinyl chloride-based polymer and method for preparing vinyl chloride-based polymer using same |
| WO2020091340A1 (en) * | 2018-10-29 | 2020-05-07 | 주식회사 엘지화학 | Method for preparing vinyl chloride-based polymer |
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| CN100417686C (en) * | 2005-11-11 | 2008-09-10 | 清华大学 | High molecule/calcium carbonate nanometer particles, functional particles and prepn. method thereof |
| CN102199233A (en) * | 2011-03-31 | 2011-09-28 | 贵州大学 | Method for polymerizing polyvinyl chloride (PVC) resin by virtue of in-situ suspension |
| CN103242608B (en) * | 2013-06-03 | 2015-04-08 | 鸡东县华鑫塑料制品有限公司 | Polymer energy-saving environment-friendly rare earth composite PVC (Polyvinyl Chloride) resin special material |
| CN104177524B (en) * | 2014-08-14 | 2016-01-27 | 杭州华纳化工有限公司 | A kind of graphene/nanometer calcium carbonate/vinylchlorid terpolymer resin in-situ suspension polymerization method |
| CN105418813A (en) * | 2015-12-19 | 2016-03-23 | 仇颖超 | Preparation method of functional nano calcium carbonate reinforced polyvinyl chloride resin |
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| WO2020091429A1 (en) * | 2018-11-02 | 2020-05-07 | 주식회사 엘지화학 | Composition for preparing vinyl chloride-based polymer and method for preparing vinyl chloride-based polymer using same |
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