CN102964509A - Nano titania impact resistant modified acrylate polymer and preparation method thereof - Google Patents
Nano titania impact resistant modified acrylate polymer and preparation method thereof Download PDFInfo
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- CN102964509A CN102964509A CN2012105142461A CN201210514246A CN102964509A CN 102964509 A CN102964509 A CN 102964509A CN 2012105142461 A CN2012105142461 A CN 2012105142461A CN 201210514246 A CN201210514246 A CN 201210514246A CN 102964509 A CN102964509 A CN 102964509A
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Abstract
The invention relates to a nano titania 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 titania 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 titania 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 titanium oxide 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 titanium oxide 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 titanium oxide impact modified acrylic ester family macromolecule polymkeric substance provided by the invention in the polymerization single polymerization monomer polymerization process, adds nano titanium oxide 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 10 ~ the 50nm of the particle diameter of nano titanium oxide.The nano titanium oxide consumption is 0.1 ~ 20% of polymerization single polymerization monomer gross weight.Nano titanium oxide can be in polymkeric substance Uniform Dispersion, present small-size effect and surface effects, play the enhancing toughening effect, the physical crosslinking density of acrylic resin is increased, improve its shock resistance, the PVC section bar erosion-resisting characteristics of preparing thus is high.
The preparation method of nano titanium oxide 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, 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 titanium oxide;
(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 titanium oxide.
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 Potassium 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 titanium oxide 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 Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, (particle diameter is 30 ± 5nm) 1 kilograms to nano titanium oxide.
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 titanium oxide and 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 titanium oxide 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 11.5, 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 Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, (particle diameter is 40 ± 5nm) 5 kilograms to nano titanium oxide.
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, 300 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 titanium oxide and 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 65 ℃, is closed temperature lowering water, when treating that temperature in the kettle drops to 48 ℃ naturally, and blowing, drying becomes pulverous nano titanium oxide 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 11.3, 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 Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, (particle diameter is 45 ± 5nm) 10 kilograms to nano titanium oxide.
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, 700 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 titanium oxide and 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 60 ℃, is closed temperature lowering water, when treating that temperature in the kettle drops to 46 ℃ naturally, and blowing, drying becomes pulverous nano titanium oxide 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 Potassium Persulphate, 1 kilogram of sodium lauryl sulphate, (particle diameter is 25 ± 5nm) 25 kilograms to nano titanium oxide.
Embodiment 4 preparation methods such as embodiment 1 obtain nano titanium oxide 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 Potassium Persulphates, 5 kilograms of sodium lauryl sulphate, (particle diameter is 15 ± 5nm) 50 kilograms to nano titanium oxide.
Embodiment 5 preparation methods such as embodiment 1 obtain nano titanium oxide 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 Potassium Persulphates, 10 kilograms of Sodium dodecylbenzene sulfonatees, (particle diameter is 20 ± 5nm) 100 kilograms to nano titanium oxide.
Embodiment 6 preparation methods such as embodiment 1 obtain nano titanium oxide 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: 1500 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 4 kilograms of Potassium Persulphates, 15 kilograms of Sodium dodecylbenzene sulfonatees, (particle diameter is 30 ± 5nm) 200 kilograms to nano titanium oxide.
Embodiment 7 preparation methods such as embodiment 1 obtain nano titanium oxide 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) 150 kilograms to nano titanium oxide.
Embodiment 8 preparation methods such as embodiment 1 obtain nano titanium oxide 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) 50 kilograms to nano titanium oxide.
Embodiment 9 preparation methods such as embodiment 1 obtain nano titanium oxide 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 10 ± 5nm) 50 kilograms to nano titanium oxide.
Embodiment 10 preparation methods such as embodiment 1 obtain nano titanium oxide 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 Potassium Persulphate, 30 kilograms of sodium laurylsulfonates, (particle diameter is 40 ± 5nm) 50 kilograms to nano titanium oxide.
Embodiment 11 preparation methods such as embodiment 1 obtain nano titanium oxide 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 Potassium Persulphate, 36 kilograms of sodium laurylsulfonates, (particle diameter is 30 ± 5nm) 50 kilograms to nano titanium oxide.
Embodiment 12 preparation methods such as embodiment 1 obtain nano titanium oxide 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
Raw material: 1500 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 1 kilogram of Potassium 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 titanium 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 titanium oxide 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 titanium oxide impact modified acrylic ester family macromolecule polymkeric substance is characterized in that: in the polymerization single polymerization monomer polymerization process, add nano titanium oxide and make, wherein: polymerization single polymerization monomer is methyl methacrylate and butyl acrylate.
2. nano titanium oxide 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 titanium oxide impact modified acrylic ester family macromolecule polymkeric substance according to claim 1 is characterized in that: the preferred 10 ~ 50nm of the particle diameter of nano titanium oxide.
4. nano titanium oxide impact modified acrylic ester family macromolecule polymkeric substance according to claim 1, it is characterized in that: the nano titanium oxide consumption is 0.1 ~ 20% of polymerization single polymerization monomer gross weight.
5. the preparation method of a nano titanium oxide 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 titanium oxide;
(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 titanium oxide 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 titanium oxide 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 titanium oxide impact modified acrylic ester family macromolecule polymkeric substance according to claim 5, it is characterized in that: 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.
9. the preparation method of nano titanium oxide impact modified acrylic ester family macromolecule polymkeric substance according to claim 5, it is characterized in that: initiator is Potassium Persulphate or Sodium Persulfate in the step (1), and initiator amount is 0.05 ~ 0.5% of polymerization single polymerization monomer gross weight.
10. the preparation method of nano titanium oxide 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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| CN102516477A (en) * | 2011-11-23 | 2012-06-27 | 华南理工大学 | Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof |
| CN103183770A (en) * | 2011-12-30 | 2013-07-03 | 山东世拓高分子材料股份有限公司 | Nano-titania-modified acrylate linear high-molecular polymer and preparation method thereof |
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Patent Citations (4)
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| US20050282946A1 (en) * | 2004-06-21 | 2005-12-22 | Tyau-Jeen Lin | Titanium dioxide slurries for ink applications |
| CN101108886A (en) * | 2007-08-13 | 2008-01-23 | 中国林业科学研究院木材工业研究所 | Aquosity wood lacquer emulsions and wood lacquer of the same |
| CN102516477A (en) * | 2011-11-23 | 2012-06-27 | 华南理工大学 | Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof |
| CN103183770A (en) * | 2011-12-30 | 2013-07-03 | 山东世拓高分子材料股份有限公司 | Nano-titania-modified acrylate linear high-molecular polymer and preparation method thereof |
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