CN103012659B - Nano-calcium-carbonate modified impact-resisting acrylate high-molecular polymer and method for preparing same - Google Patents
Nano-calcium-carbonate modified impact-resisting acrylate high-molecular polymer and method for preparing same Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title abstract description 8
- 238000000034 method Methods 0.000 title abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 5
- 229960003563 calcium carbonate Drugs 0.000 title abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 230000007423 decrease Effects 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229920002521 macromolecule Polymers 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- -1 modified acrylic ester Chemical class 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 25
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 25
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract description 3
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003607 modifier Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- AHVOFPQVUVXHNL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C=C AHVOFPQVUVXHNL-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- NNJPGOLRFBJNIW-HNNXBMFYSA-N (-)-demecolcine Chemical compound C1=C(OC)C(=O)C=C2[C@@H](NC)CCC3=CC(OC)=C(OC)C(OC)=C3C2=C1 NNJPGOLRFBJNIW-HNNXBMFYSA-N 0.000 description 1
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 description 1
- 241000143437 Aciculosporium take Species 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
Abstract
The invention relates to a nano-calcium-carbonate modified impact-resisting acrylate high-molecular polymer and a method for preparing the same, belonging to the technical field of PVC (polyvinyl chloride) processing aid. The nano-calcium-carbonate modified impact-resisting acrylate high-molecular polymer is prepared by adding nano calcium carbonate in the polymerizing process of polymerized monomers, wherein the polymerized monomers are methyl methacrylate and butyl acrylate. The method comprises the following steps: adding water into a reactor, starting to stir, adding an emulsifying agent and the polymerizing monomers, heating to 65-68 DEG C, adding an initiating agent to react, starting a temperature decreasing water to decrease temperature when the temperature in the reactor beings to increase, adding nano calcium carbonate when the temperature in the reactor decreases from the peak temperature, turning off the temperature decreasing water when the temperature in the reactor decreases to 60-65 DEG C, and discharging when the temperature in the reactor decreases to 45-48 DEG C naturally, and drying to obtain the powdery product. The acrylic polymer has low cost, and the particles have good fluidity. The PVC profile prepared from the nano-calcium-carbonate modified impact-resisting acrylate high-molecular polymer has high impact resistance. The method is simple and practical and is easy to implement.
Description
Technical field
The present invention relates to a kind of nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance and preparation method thereof, belong to PVC processing aid technical field.
Background technology
PVC processing aid of the prior art, general normal employing esters of acrylic acid linear macromolecule polymkeric substance, be methyl methacrylate-butyl acrylate multipolymer, this copolymer pellet state mobility is general, cost is high.General polyvinyl chloride resin is about 7000 ~ 9000 yuan/ton, methyl methacrylate-butyl acrylate multipolymer price is 20000 ~ 25000 yuan/ton, this price changes along with oil price and constantly changes, this auxiliary agent is on the high side for polyvinyl chloride resin, thus make the cost increase of the PVC product produced, the PVC profile mobility adopting this kind of multipolymer to prepare in addition and erosion-resisting characteristics general.
Summary of the invention
The object of this invention is to provide a kind of nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance, as PVC auxiliary agent, cost is low, and graininess good fluidity, the PVC profile erosion-resisting characteristics prepared thus is high; And a kind of its preparation method is provided, preparation method is simple, easy to implement.
Nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance provided by the invention, in polymerization single polymerization monomer polymerization process, adds nano-calcium carbonate and makes, wherein: polymerization single polymerization monomer is methyl methacrylate and butyl acrylate.
Wherein:
The weight ratio of methyl methacrylate and butyl acrylate is 1:0 ~ 3.
The particle diameter preferably 10 ~ 100nm of nano-calcium carbonate.Nano-calcium carbonate consumption is 0.5 ~ 5% of polymerization single polymerization monomer gross weight.Nano-calcium carbonate can be dispersed in the polymer, and have more reinforcing, and improve the shock resistance of polymkeric substance, the PVC profile erosion-resisting characteristics prepared thus is high.
The preparation method of nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance provided by the invention, comprises the following steps:
(1) in reactor, add water, open and stir, add emulsifying agent, one-step polymerization monomer, open heating, when reactor temperature reaches 65 ~ 68 DEG C, add initiator, reaction;
(2) when reactor temperature starts to rise, open temperature lowering water cooling, when temperature rise to summit start to decline time, in still, add remaining two sections of monomers and nano-calcium carbonate;
(3) when temperature continues to drop to 60 ~ 65 DEG C, temperature lowering water is closed, when temperature in the kettle drops to 45 ~ 48 DEG C naturally, blowing, dry, obtain powdery product.
Wherein:
In order to regulate temperature better and make reaction more stable, polymerization single polymerization monomer divides two sections or multistage to add in step (1), and points two sections add fashionable, and one section is 30 ~ 70:30 ~ 70 with the weight ratio of two sections, one section adds with emulsifying agent simultaneously, and two sections add with nano-calcium carbonate simultaneously.
In step (1), mixing speed is 60 ~ 75 revs/min.
In step (1), emulsifying agent is sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or OP-10, and emulsifier is 0.1 ~ 3.6% of polymerization single polymerization monomer gross weight.
In step (1), initiator is Sodium Persulfate or ammonium persulphate, and initiator amount is 0.05 ~ 0.5% of polymerization single polymerization monomer gross weight.
In step (1), the consumption of water is 1.3 ~ 1.6 times of polymerization single polymerization monomer gross weight.
Compared with prior art, the present invention has the following advantages:
(1) nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance is adopted, i.e. processed-type esters of acrylic acid linear polymeric polymkeric substance, this acrylic polymer cost is low, and graininess good fluidity, the PVC profile erosion-resisting characteristics prepared thus is high.
(2) preparation method of the present invention is simple, easy to implement.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Raw material: softening water 1500 kilograms, the polymeric monomer composite 1000 kilograms that 600 kilograms of methyl methacrylates and 400 kilograms of butyl acrylates are uniformly mixed into, Sodium Persulfate 1 kilogram, sodium laurylsulfonate 15 kilograms, nano-calcium carbonate (particle diameter is 20 ± 5nm) 5 kilograms.
Preparation method: the softening water adding set amount in glassed steel reaction vessels, opens and stirs, mixing speed 75 revs/min, add emulsifying agent, 480 kilograms of polymeric monomer composites, capping still, open heating, when reactor temperature reaches 65 DEG C, add initiator, carry out one section of reaction.When reactor temperature rises, in reactor, polyreaction starts, and now opens temperature lowering water cooling.When temperature rises to about 78 DEG C, no longer rise, and when starting to drop to 70 DEG C, in still, add nano-calcium carbonate and surplus 520 kilograms of two sections of monomer compositions, carry out second-stage reaction, in reaction, temperature controls below 80 DEG C.Reacted rear temperature to decline, when dropping to 63 DEG C, close temperature lowering water, when temperature in the kettle drops to 45 DEG C naturally, blowing, drying becomes pulverous nano-calcium carbonate impact modified acrylic ester family macromolecule polymer A.Take chloroform as solvent, measure at 25 ± 0.1 DEG C of temperature, find that its limiting viscosity is 11.6, hereinafter referred to as modifier A.
Embodiment 2
Raw material: softening water 1500 kilograms, methyl methacrylate 600 kilograms, butyl acrylate 400 kilograms, ammonium persulphate 0.5 kilogram, sodium lauryl sulphate 15 kilograms, nano-calcium carbonate (particle diameter is 30 ± 5nm) 10 kilograms.
Preparation method: the softening water adding set amount in glassed steel reaction vessels, opens and stirs, mixing speed 60 revs/min, add emulsifying agent, 700 kilograms of polymeric monomer composites, capping still, open heating, when reactor temperature reaches 66 DEG C, add initiator, carry out one section of reaction.When reactor temperature rises, in reactor, polyreaction starts, and now opens temperature lowering water cooling.When temperature rises to about 77 DEG C, no longer rise, and when starting to drop to 70 DEG C, in still, add nano-calcium carbonate and surplus 300 kilograms of two sections of monomer compositions, carry out second-stage reaction, in reaction, temperature controls below 80 DEG C.Reacted rear temperature to decline, when dropping to 65 DEG C, close temperature lowering water, when temperature in the kettle drops to 48 DEG C naturally, blowing, drying becomes pulverous nano-calcium carbonate impact modified acrylic ester family macromolecule polymer B.Take chloroform as solvent, measure at 25 ± 0.1 DEG C of temperature, find that its limiting viscosity is 11.1, hereinafter referred to as properties-correcting agent B.
Embodiment 3
Raw material: softening water 1600 kilograms, methyl methacrylate 600 kilograms, butyl acrylate 400 kilograms, Sodium Persulfate 5 kilograms, Sodium dodecylbenzene sulfonate 15 kilograms, nano-calcium carbonate (particle diameter is 50 ± 5nm) 20 kilograms.
Preparation method: the softening water adding set amount in glassed steel reaction vessels, opens and stirs, mixing speed 68 revs/min, add emulsifying agent, 300 kilograms of polymeric monomer composites, capping still, open heating, when reactor temperature reaches 68 DEG C, add initiator, carry out one section of reaction.When reactor temperature rises, in reactor, polyreaction starts, and now opens temperature lowering water cooling.When temperature rises to about 78 DEG C, no longer rise, and when starting to drop to 70 DEG C, in still, add nano-calcium carbonate and surplus 700 kilograms of two sections of monomer compositions, carry out second-stage reaction, in reaction, temperature controls below 80 DEG C.Reacted rear temperature to decline, when dropping to 60 DEG C, close temperature lowering water, when temperature in the kettle drops to 46 DEG C naturally, blowing, drying becomes pulverous nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance C.Take chloroform as solvent, measure at 25 ± 0.1 DEG C of temperature, find that its limiting viscosity is 10.8, hereinafter referred to as properties-correcting agent C.
Embodiment 4
Raw material: softening water 1300 kilograms, methyl methacrylate 600 kilograms, butyl acrylate 400 kilograms, Sodium Persulfate 1 kilogram, OP-101 kilogram, nano-calcium carbonate (particle diameter is 80 ± 5nm) 30 kilograms.
Embodiment 4 preparation method, as embodiment 1, obtains nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance D, take chloroform as solvent, measure at 25 ± 0.1 DEG C of temperature, find that its limiting viscosity is 10.4, hereinafter referred to as properties-correcting agent D.
Embodiment 5
Raw material: softening water 1500 kilograms, methyl methacrylate 1000 kilograms, Sodium Persulfate 2 kilograms, sodium lauryl sulphate 5 kilograms, nano-calcium carbonate (particle diameter is 100 ± 5nm) 50 kilograms.
Embodiment 5 preparation method, as embodiment 1, obtains nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance E, take chloroform as solvent, measure at 25 ± 0.1 DEG C of temperature, find that its limiting viscosity is 10.0, hereinafter referred to as properties-correcting agent E.
Embodiment 6
Raw material: softening water 1500 kilograms, methyl methacrylate 250 kilograms, butyl acrylate 750 kilograms, Sodium Persulfate 3 kilograms, Sodium dodecylbenzene sulfonate 15 kilograms, nano-calcium carbonate (particle diameter is 10 ± 5nm) 40 kilograms.
Embodiment 6 preparation method, as embodiment 1, obtains nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance F, take chloroform as solvent, measure at 25 ± 0.1 DEG C of temperature, find that its limiting viscosity is 9.6, hereinafter referred to as properties-correcting agent F.
Comparative example 1
Softening water 1500 kilograms, methyl methacrylate 600 kilograms, butyl acrylate 400 kilograms, Sodium Persulfate 1 kilogram, sodium laurylsulfonate 15 kilograms, in comparative example 1 preparation method, except not plus nano calcium carbonate, all the other are as embodiment 1, obtain modification acrylate family macromolecule polymkeric substance M, take chloroform as solvent, measure at 25 ± 0.1 DEG C of temperature, find that its limiting viscosity is 9.1, hereinafter referred to as properties-correcting agent M.
Experimental result is as follows:
Performance Indexs measure is carried out to embodiment 1 ~ 6 and comparative example 1 and Cost Evaluation as shown in table 1 below, wherein cost keeping is according to the market value of in late October, 2012.
Table 1 polymer performance index and cost table
Note: ★ more multilist shows that graininess mobility is better.
2, the mensuration of PVC product erosion-resisting characteristics:
Base material formulation is as follows, and Ge Zu unit is kg:
Get 1kg modifier A to join in above base material formulation, make test material 1.;
Get 2kg modifier A to join in above base material formulation, make test material 2.;
Get 5kg modifier A to join in above base material formulation, make test material 3.;
Get 1kg properties-correcting agent M to join in above base material formulation, make test material I;
Get 2kg properties-correcting agent M to join in above base material formulation, make test material II;
Get 5kg properties-correcting agent M to join in above base material formulation, make test material III.
Above-mentioned each component is joined in high-speed mixer, opens and stir, when temperature is elevated to 110 DEG C, cooling blowing, when temperature is reduced to room temperature, is placed on double roller plastic-making device, at 190 DEG C, open refining 4 minutes, pull into sheet material, then by the thickness requirement of test, at vulcanizing press, at 190 DEG C, under the condition of 15MPa, tabletted, obtain PVC sheet 1. ~ 3. with PVC sheet I ~ III, test its simple beam impact strength according to the requirement of GB/T1403, result is as shown in table 2 below:
The shock strength table of the PVC sheet that table 2 is prepared
| PVC sheet 1. | PVC sheet 2. | PVC sheet 3. | |
| -10 DEG C of single notched Izod impact strength (KJ/m 2） | 4.67 | 4.93 | 6.25 |
| PVC sheet I | PVC sheet II | PVC sheet III | |
| -10 DEG C of single notched Izod impact strength (KJ/m 2） | 3.48 | 3.91 | 4.72 |
From table 2 data analysis, the PVC profile erosion-resisting characteristics adopting nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance to prepare obviously is better than the PVC profile prepared with common modifications agent.And under the condition that erosion-resisting characteristics is similar, the polymkeric substance cost that this method uses reduces.
Claims (1)
1. a preparation method for nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance, is characterized in that: comprise the following steps:
The softening water of set amount is added in glassed steel reaction vessels, open and stir, mixing speed 75 revs/min, add emulsifying agent, 480 kilograms of polymeric monomer composites, capping still, open heating, when reactor temperature reaches 65 DEG C, add initiator, carry out one section of reaction, when reactor temperature rises, in reactor, polyreaction starts, now open temperature lowering water cooling, when temperature rises to 78 DEG C, no longer rise, and when starting to drop to 70 DEG C, nano-calcium carbonate and surplus 520 kilograms of two sections of monomer compositions are added in still, carry out second-stage reaction, in reaction, temperature controls below 80 DEG C, react rear temperature to decline, when dropping to 63 DEG C, close temperature lowering water, when temperature in the kettle drops to 45 DEG C naturally, blowing, drying becomes pulverous nano-calcium carbonate impact modified acrylic ester family macromolecule polymkeric substance,
Comprise following raw material: softening water 1500 kilograms, the polymeric monomer composite 1000 kilograms that 600 kilograms of methyl methacrylates and 400 kilograms of butyl acrylates are uniformly mixed into, initiator is Sodium Persulfate 1 kilogram, emulsifying agent is sodium laurylsulfonate 15 kilograms, nano-calcium carbonate 5 kilograms, the particle diameter of nano-calcium carbonate is 20 ± 5nm.
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| CN105218966A (en) * | 2015-07-22 | 2016-01-06 | 滁州远方车船装备工程有限公司 | A kind of low temperature resistant PVC board and preparation method thereof |
| CN109456658B (en) * | 2018-11-14 | 2021-03-19 | 广东爱迪斯新型材料科技股份有限公司 | Back water pressure reverse leakage waterproof coating and preparation method thereof |
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