CN102964508A - Nano silica impact resistant modified acrylate polymer and preparation method thereof - Google Patents
Nano silica impact resistant modified acrylate polymer and preparation method thereof Download PDFInfo
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- CN102964508A CN102964508A CN2012105142103A CN201210514210A CN102964508A CN 102964508 A CN102964508 A CN 102964508A CN 2012105142103 A CN2012105142103 A CN 2012105142103A CN 201210514210 A CN201210514210 A CN 201210514210A CN 102964508 A CN102964508 A CN 102964508A
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Abstract
The invention relates to a nano silica 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 silica 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 nano silica 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 silicon 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 is the methyl methacrylate-butyl acrylate multipolymer, this copolymer pellet state is mobile generally, cost is high.General polyvinyl chloride resin is about 7000 ~ 9000 yuan/tons, methyl methacrylate-butyl acrylate multipolymer price is 20000 ~ 25000 yuan/tons, this price changes and constantly changes along with oil price, this auxiliary agent is on the high side for polyvinyl chloride resin, thereby so that the cost of the PVC goods of producing rises, the PVC section bar that adopts in addition this kind multipolymer to prepare is mobile and erosion-resisting characteristics is general.
Summary of the invention
The purpose of this invention is to provide a kind of nano silicon impact modified acrylic ester family macromolecule polymkeric substance, as the PVC auxiliary agent, cost is low, and the graininess good fluidity, and the PVC section bar erosion-resisting characteristics of preparing thus is high; And a kind of its preparation method is provided, the preparation method is simple, and is easy to implement.
Nano silicon impact modified acrylic ester family macromolecule polymkeric substance provided by the invention in the polymerization single polymerization monomer polymerization process, adds nano silicon and makes, and 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.
Preferred 20 ~ the 50nm of the particle diameter of nano silicon.The nano silicon consumption is 0.1 ~ 2% of polymerization single polymerization monomer gross weight.Nano silicon can be in polymkeric substance Uniform Dispersion, present small-size effect and surface effects, play the enhancing toughening effect, the PVC section bar erosion-resisting characteristics of preparing thus is high.
The preparation method of nano silicon impact modified acrylic ester family macromolecule polymkeric substance provided by the invention may further comprise the steps:
(1) in reactor, adds entry, open and stir, add emulsifying agent, one-step polymerization monomer, open heating, when reactor temperature reaches 65 ~ 68 ℃, add initiator, reaction;
(2) when reactor temperature begins to rise, open the temperature lowering water cooling, when temperature rises to the summit and begins to descend, in still, add remaining two sections monomers and nano silicon;
(3) when temperature continues to drop to 60 ~ 65 ℃, close temperature lowering water, when treating that temperature in the kettle drops to 45 ~ 48 ℃ naturally, blowing, drying obtains powdery product.
Wherein:
In order to regulate better temperature and to make reaction more stable, polymerization single polymerization monomer divides two sections or multistage to add in the step (1), and minutes two sections add fashionablely, and one section weight ratio with two sections is 30 ~ 70:30 ~ 70, one section adds simultaneously with emulsifying agent, and two sections add simultaneously with nano silicon.
Mixing speed is 60 ~ 75 rev/mins in the step (1).
Emulsifying agent is sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or OP-10 in the step (1), and emulsifier is 0.1 ~ 3.6% of polymerization single polymerization monomer gross weight.
Initiator is ammonium persulphate or Sodium Persulfate in the step (1), and initiator amount is 0.05 ~ 0.5% of polymerization single polymerization monomer gross weight.
The consumption of the middle water of step (1) 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) adopts nano silicon impact modified acrylic ester family macromolecule polymkeric substance, it is processed-type esters of acrylic acid linear polymeric polymkeric substance, this acrylic polymer cost is low, and the graininess good fluidity, and the PVC section bar erosion-resisting characteristics of preparing thus is high.
(2) preparation method of the present invention is simple, and is easy to implement.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
Raw material: 1500 kilograms of softening waters, 1000 kilograms of the polymeric monomer composites that 600 kilograms of methyl methacrylates and 400 kilograms of butyl acrylates are uniformly mixed into, 1 kilogram of ammonium persulphate, 15 kilograms of sodium laurylsulfonates, (particle diameter is 30 ± 5nm) 1 kilograms to nano silicon.
Preparation method: add the softening water of set amount in the glassed steel reaction vessels, open and stir, 75 rev/mins of mixing speed, add emulsifying agent, 480 kilograms of polymeric monomer composites, the capping still is opened heating, when reactor temperature reaches 65 ℃, add initiator, carry out one section reaction.When reactor temperature rose, polyreaction began in the reactor, opened the temperature lowering water cooling this moment.When temperature rises to about 78 ℃, no longer rise, and when beginning to drop to 70 ℃, in still, add nano silicon and surplus 520 kilograms of two sections monomer compositions, carry out second-stage reaction, temperature is controlled at below 80 ℃ in the reaction.Drop in temperature after reaction is finished when dropping to 63 ℃, is closed temperature lowering water, when treating that temperature in the kettle drops to 45 ℃ naturally, and blowing, drying becomes pulverous nano silicon impact modified acrylic ester family macromolecule polymer A.Take chloroform as solvent, under 25 ± 0.1 ℃ of temperature, measure, find that its limiting viscosity is 11.7, hereinafter to be referred as modifier A.
Embodiment 2
Raw material: 1500 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 1 kilogram of ammonium persulphate, 15 kilograms of sodium laurylsulfonates, (particle diameter is 40 ± 5nm) 2 kilograms to nano silicon.
Preparation method: add the softening water of set amount in the glassed steel reaction vessels, open and stir, 60 rev/mins of mixing speed, add emulsifying agent, 700 kilograms of polymeric monomer composites, the capping still is opened heating, when reactor temperature reaches 66 ℃, add initiator, carry out one section reaction.When reactor temperature rose, polyreaction began in the reactor, opened the temperature lowering water cooling this moment.When temperature rises to about 77 ℃, no longer rise, and when beginning to drop to 70 ℃, in still, add nano silicon and surplus 300 kilograms of two sections monomer compositions, carry out second-stage reaction, temperature is controlled at below 80 ℃ in the reaction.Drop in temperature after reaction is finished when dropping to 65 ℃, is closed temperature lowering water, when treating that temperature in the kettle drops to 48 ℃ naturally, and blowing, drying becomes pulverous nano silicon impact modified acrylic ester family macromolecule polymer B.Take chloroform as solvent, under 25 ± 0.1 ℃ of temperature, measure, find that its limiting viscosity is 11.4, hereinafter to be referred as properties-correcting agent B.
Embodiment 3
Raw material: 1500 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 1 kilogram of ammonium persulphate, 15 kilograms of sodium laurylsulfonates, (particle diameter is 45 ± 5nm) 5 kilograms to nano silicon.
Preparation method: add the softening water of set amount in the glassed steel reaction vessels, open and stir, 68 rev/mins of mixing speed, add emulsifying agent, 300 kilograms of polymeric monomer composites, the capping still is opened heating, when reactor temperature reaches 68 ℃, add initiator, carry out one section reaction.When reactor temperature rose, polyreaction began in the reactor, opened the temperature lowering water cooling this moment.When temperature rises to about 78 ℃, no longer rise, and when beginning to drop to 70 ℃, in still, add nano silicon and surplus 700 kilograms of two sections monomer compositions, carry out second-stage reaction, temperature is controlled at below 80 ℃ in the reaction.Drop in temperature after reaction is finished when dropping to 60 ℃, is closed temperature lowering water, when treating that temperature in the kettle drops to 46 ℃ naturally, and blowing, drying becomes pulverous nano silicon impact modified acrylic ester family macromolecule polymkeric substance C.Take chloroform as solvent, under 25 ± 0.1 ℃ of temperature, measure, find that its limiting viscosity is 11.2, hereinafter to be referred as properties-correcting agent C.
Embodiment 4
Raw material: 1300 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 0.5 kilogram of ammonium persulphate, 1 kilogram of sodium lauryl sulphate, (particle diameter is 25 ± 5nm) 10 kilograms to nano silicon.
Embodiment 4 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance D, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 11.0, hereinafter to be referred as properties-correcting agent D.
Embodiment 5
Raw material: 1500 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 2 kilograms of ammonium persulphates, 5 kilograms of sodium lauryl sulphate, (particle diameter is 20 ± 5nm) 15 kilograms to nano silicon.
Embodiment 5 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance E, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 10.8, hereinafter to be referred as properties-correcting agent E.
Embodiment 6
Raw material: 1400 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 3 kilograms of ammonium persulphates, 10 kilograms of Sodium dodecylbenzene sulfonatees, (particle diameter is 50 ± 5nm) 20 kilograms to nano silicon.
Embodiment 6 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance F, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 10.7, hereinafter to be referred as properties-correcting agent F.
Embodiment 7
Raw material: 1300 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 4 kilograms of ammonium persulphates, 15 kilograms of Sodium dodecylbenzene sulfonatees, (particle diameter is 30 ± 5nm) 5 kilograms to nano silicon.
Embodiment 7 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance G, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 10.5, hereinafter to be referred as properties-correcting agent G.
Embodiment 8
Raw material: 1600 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 5 kilograms of Sodium Persulfates, 20 kilograms of Sodium dodecylbenzene sulfonatees, (particle diameter is 30 ± 5nm) 10 kilograms to nano silicon.
Embodiment 8 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance H, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 10.3, hereinafter to be referred as properties-correcting agent H.
Embodiment 9
Raw material: 1300 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 5 kilograms of Sodium Persulfates, the OP-1020 kilogram, (particle diameter is 50 ± 5nm) 5 kilograms to nano silicon.
Embodiment 9 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance I, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 10.2, hereinafter to be referred as properties-correcting agent I.
Embodiment 10
Raw material: 1600 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 3 kilograms of Sodium Persulfates, the OP-1025 kilogram, (particle diameter is 20 ± 5nm) 10 kilograms to nano silicon.
Embodiment 10 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance J, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 10.0, hereinafter to be referred as properties-correcting agent J.
Embodiment 11
Raw material: 1500 kilograms of softening waters, 1000 kilograms of methyl methacrylates, 1 kilogram of ammonium persulphate, 30 kilograms of sodium laurylsulfonates, (particle diameter is 40 ± 5nm) 10 kilograms to nano silicon.
Embodiment 11 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance K, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 9.7, hereinafter to be referred as properties-correcting agent K.
Embodiment 12
Raw material: 1500 kilograms of softening waters, 250 kilograms of methyl methacrylates, 750 kilograms of butyl acrylates, 1 kilogram of ammonium persulphate, 36 kilograms of sodium laurylsulfonates, (particle diameter is 30 ± 5nm) 20 kilograms to nano silicon.
Embodiment 12 preparation methods such as embodiment 1 obtain nano silicon impact modified acrylic ester family macromolecule polymkeric substance L, take chloroform as solvent, measure under 25 ± 0.1 ℃ of temperature, find that its limiting viscosity is 9.4, hereinafter to be referred as modifer L.
Comparative Examples 1
1500 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 1 kilogram of ammonium persulphate, 15 kilograms of sodium laurylsulfonates, among Comparative Examples 1 preparation method, except all the other obtain modification acrylate family macromolecule polymkeric substance M such as embodiment 1 the plus nano silicon-dioxide not, take chloroform as solvent, under 25 ± 0.1 ℃ of temperature, measure, find that its limiting viscosity is 9.1, hereinafter to be referred as properties-correcting agent M.
Experimental result is as follows:
Embodiment 1 ~ 12 and Comparative Examples 1 carried out performance index detect and Cost Evaluation is 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
Annotate: ★ more multilist shows that the graininess flowability is better.
2, the mensuration of PVC goods erosion-resisting characteristics:
Base material formulation is as follows, and each unit of group is kg:
Get the 1kg modifier A and join in the above base material formulation, make the test material 1.;
Get the 2kg modifier A and join in the above base material formulation, make the test material 2.;
Get the 5kg modifier A and join in the above base material formulation, make the test material 3.;
Get 1kg properties-correcting agent M and join in the above base material formulation, make test material I;
Get 2kg properties-correcting agent M and join in the above base material formulation, make test material II;
Get 5kg properties-correcting agent M and join in the above base material formulation, make test material III.
Above-mentioned each component is joined in the high-speed mixer, open and stir, when temperature is elevated to 110 ℃, the cooling blowing when temperature is reduced to room temperature, places on the double roller plastic-making device, under 190 ℃, open refining 4 minutes, pull into sheet material, then by the thickness requirement of testing, at vulcanizing press, at 190 ℃, under the condition of 15MPa, compacting in flakes, obtain the PVC sheet 1. ~ 3. with PVC sheet I ~ III, test its simple beam impact strength according to the requirement of GB/T1403, the result is as shown in table 2 below:
The shock strength table of the PVC sheet that table 2 is prepared
| ? | The PVC sheet 1. | The PVC sheet 2. | The PVC sheet 3. |
| -10 ℃ of single notched Izod impact strength (KJ/m 2） | 4.63 | 4.95 | 6.28 |
| ? | PVC sheet I | PVC sheet II | PVC sheet III |
| -10 ℃ of single notched Izod impact strength (KJ/m 2） | 3.44 | 3.97 | 4.75 |
By table 2 data analysis as can be known, the PVC section bar erosion-resisting characteristics that adopts nano silicon impact modified acrylic ester family macromolecule polymkeric substance to prepare obviously is better than the PVC section bar with common properties-correcting agent preparation.And under the similar condition of erosion-resisting characteristics, the polymkeric substance cost that this method is used.
Claims (10)
1. nano silicon impact modified acrylic ester family macromolecule polymkeric substance is characterized in that: in the polymerization single polymerization monomer polymerization process, add nano silicon and make, wherein: polymerization single polymerization monomer is methyl methacrylate and butyl acrylate.
2. nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 1, it is characterized in that: the weight ratio of methyl methacrylate and butyl acrylate is 1:0 ~ 3.
3. nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 1 is characterized in that: the preferred 20 ~ 50nm of the particle diameter of nano silicon.
4. nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 1, it is characterized in that: the nano silicon consumption is 0.1 ~ 2% of polymerization single polymerization monomer gross weight.
5. the preparation method of a nano silicon impact modified acrylic ester family macromolecule polymkeric substance claimed in claim 1 is characterized in that: may further comprise the steps:
(1) in reactor, adds entry, open and stir, add emulsifying agent, polymerization single polymerization monomer, open heating, when reactor temperature reaches 65 ~ 68 ℃, add initiator, reaction;
(2) when reactor temperature begins to rise, open the temperature lowering water cooling, when temperature rises to the summit and begins to descend, in still, add nano silicon;
(3) when temperature continues to drop to 60 ~ 65 ℃, close temperature lowering water, when treating that temperature in the kettle drops to 45 ~ 48 ℃ naturally, blowing, drying obtains powdery product.
6. the preparation method of nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 5 is characterized in that: polymerization single polymerization monomer divides two sections or multistage to add in the step (1).
7. the preparation method of nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 5 is characterized in that: mixing speed is 60 ~ 75 rev/mins in the step (1).
8. the preparation method of nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 5, it is characterized in that: the emulsifying agent described in the step (1) 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.
9. the preparation method of nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 5, it is characterized in that: the initiator described in the step (1) is ammonium persulphate or Sodium Persulfate, and initiator amount is 0.05 ~ 0.5% of polymerization single polymerization monomer gross weight.
10. the preparation method of nano silicon impact modified acrylic ester family macromolecule polymkeric substance according to claim 5, it is characterized in that: the consumption of the water described in the step (1) is 1.3 ~ 1.6 times of polymerization single polymerization monomer gross weight.
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| JP2004323634A (en) * | 2003-04-23 | 2004-11-18 | Nissan Motor Co Ltd | Nano-composite acrylic resin composition and its preparation method |
| CN1775819A (en) * | 2005-11-30 | 2006-05-24 | 中国林业科学研究院林产化学工业研究所 | Method for preparing nano silicon dioxide-acrylate polymeric microball material |
| CN101016399A (en) * | 2007-03-02 | 2007-08-15 | 中山大学 | Inorganic nano particle/polymer composite material and preparing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004323634A (en) * | 2003-04-23 | 2004-11-18 | Nissan Motor Co Ltd | Nano-composite acrylic resin composition and its preparation method |
| CN1775819A (en) * | 2005-11-30 | 2006-05-24 | 中国林业科学研究院林产化学工业研究所 | Method for preparing nano silicon dioxide-acrylate polymeric microball material |
| CN101016399A (en) * | 2007-03-02 | 2007-08-15 | 中山大学 | Inorganic nano particle/polymer composite material and preparing method thereof |
Non-Patent Citations (1)
| Title |
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| 刘磊: "ACR与SiO2杂化复合粒子的合成、表征及其改性PVC的研究", 《工程科技I辑》 * |
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