CN102964511B - Nano barium sulfate impact resistant modified acrylate polymer and preparation method thereof - Google Patents
Nano barium sulfate impact resistant modified acrylate polymer and preparation method thereof Download PDFInfo
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- CN102964511B CN102964511B CN201210517572.8A CN201210517572A CN102964511B CN 102964511 B CN102964511 B CN 102964511B CN 201210517572 A CN201210517572 A CN 201210517572A CN 102964511 B CN102964511 B CN 102964511B
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Abstract
The invention relates to a nano barium sulfate impact resistant modified acrylate polymer and a preparation method thereof, belonging to the technical field of PVC (polyvinyl chloride) processing aids. The polymer is characterized in that nano barium sulfate is added to prepare the polymer in the process of polymerizing polymer monomers, wherein the polymer monomers are methyl methacrylate and butyl acrylate. The preparation method comprises the following steps of: adding water to a reaction kettle, starting stirring, adding an emulsifier and the polymer monomers, heating the materials and adding an initiator for reaction when the temperature reaches 65-68 DEG C; opening cooling water for cooling when the temperature in the reaction kettle begins rising and adding the nano barium sulfate when the temperature begins falling after rising to the summit; and closing the cooling water when the temperature falls to 60-65 DEG C and carrying out emptying and drying when the temperature naturally falls to 45-48 DEG C, thus obtaining the powdery product. The polymer and the preparation method have the advantages that the acrylate polymer has low cost and good fluidity in the particle state; the PVC profiles prepared from the polymer have high impact resistance; and the preparation method is simple and practicable and is easy to implement.
Description
Technical field
The present invention relates to a kind of nano barium sulfate 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 barium sulfate 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 barium sulfate impact modified acrylic ester family macromolecule polymkeric substance provided by the invention, in polymerization single polymerization monomer polymerization process, adds nano barium sulfate 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 50 ~ 200nm of nano barium sulfate.Nano barium sulfate consumption is 1 ~ 5% of polymerization single polymerization monomer gross weight.Nano barium sulfate can be dispersed in the polymer, presents small-size effect and surface effects, plays activeness and quietness effect, and improve the shock resistance of polymkeric substance, the PVC profile erosion-resisting characteristics prepared thus is high.
The preparation method of nano barium sulfate 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, polymerization single 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 nano barium sulfate;
(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 described in step (1) divides two sections or multistage to add, and points two sections add fashionable, and one section is 30 ~ 50:50 ~ 70 with the weight ratio of two sections, one section adds with emulsifying agent simultaneously, and two sections add with nano barium sulfate 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 Potassium 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 barium sulfate 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 barium sulfate (particle diameter is 50 ± 5nm) 10 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, 600 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, add nano barium sulfate and 400 kilograms of two sections of monomer compositions, carry out second-stage reaction in still, 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 barium sulfate 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, Potassium Persulphate 0.5 kilogram, sodium lauryl sulphate 15 kilograms, nano barium sulfate (particle diameter is 80 ± 5nm) 20 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, add nano barium sulfate and 300 kilograms of two sections of monomer compositions, carry out second-stage reaction in still, 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 barium sulfate 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 barium sulfate (particle diameter is 100 ± 5nm) 30 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, add nano barium sulfate and 700 kilograms of two sections of monomer compositions, carry out second-stage reaction in still, 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 barium sulfate 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 barium sulfate (particle diameter is 150 ± 5nm) 40 kilograms.
Embodiment 4 preparation method, as embodiment 1, obtains nano barium sulfate 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 barium sulfate (particle diameter is 200 ± 5nm) 50 kilograms.
Embodiment 5 preparation method, as embodiment 1, obtains nano barium sulfate 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 36 kilograms, nano barium sulfate (particle diameter is 100 ± 5nm) 30 kilograms.
Embodiment 6 preparation method, as embodiment 1, obtains nano barium sulfate 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
Raw material: 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 barium sulfate, 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） | 4.69 | 4.98 | 6.53 |
| PVC sheet I | PVC sheet II | PVC sheet III | |
| -10 DEG C of single notched Izod impact strength (KJ/m 2） | 3.45 | 3.98 | 4.77 |
From table 2 data analysis, the PVC profile erosion-resisting characteristics adopting nano barium sulfate 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 barium sulfate 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, 600 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 barium sulfate and 400 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 barium sulfate 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 ammonium persulphate 1 kilogram, emulsifying agent is sodium laurylsulfonate 15 kilograms, nano barium sulfate 10 kilograms, the particle diameter of nano barium sulfate is 50 ± 5 nm.
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| CN1358786A (en) * | 2000-12-12 | 2002-07-17 | 海尔科化工程塑料国家工程研究中心有限公司 | Nano redigity impact modifying agent and preparation method |
| CN1240768C (en) * | 2003-07-22 | 2006-02-08 | 四川大学 | polyacrylic ester/inorganics I/inorganics II ternary compound particle and process for producing the same |
| KR101207124B1 (en) * | 2006-11-24 | 2012-11-30 | 주식회사 엘지화학 | Inorganic nano particle coating solution containing hydrophilic group-modified acrylic resin, and inorganic nano particle film |
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