CN102964507B - Nano ceria impact resistant modified acrylate polymer and preparation method thereof - Google Patents
Nano ceria impact resistant modified acrylate polymer and preparation method thereof Download PDFInfo
- Publication number
- CN102964507B CN102964507B CN201210514074.8A CN201210514074A CN102964507B CN 102964507 B CN102964507 B CN 102964507B CN 201210514074 A CN201210514074 A CN 201210514074A CN 102964507 B CN102964507 B CN 102964507B
- Authority
- CN
- China
- Prior art keywords
- kilograms
- temperature
- polymer
- preparation
- nano ceric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a nano ceria 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 ceria 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 ceria 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 ceric 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 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 is along with oil price changes and constantly changes, this auxiliary agent is on the high side for polyvinyl chloride resin, thereby make the cost of the PVC goods produced increase, the PVC section bar mobility and the erosion-resisting characteristics that adopt in addition this kind of multipolymer to prepare are general.
Summary of the invention
The object of this invention is to provide a kind of nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance, as PVC auxiliary agent, cost is low, and graininess good fluidity, and the PVC section bar erosion-resisting characteristics of preparing is thus high; And a kind of its preparation method is provided, preparation method is simple, easy to implement.
Nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance provided by the invention, in polymerization single polymerization monomer polymerization process, adds nano ceric oxide 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 of nano ceric oxide is 20 ~ 100nm preferably.Nano ceric oxide consumption is 0.5 ~ 5% of polymerization single polymerization monomer gross weight.Nano ceric oxide can be dispersed in polymkeric substance, presents small-size effect and surface effects, plays enhancing toughening effect, improves the shock resistance of polymkeric substance, and the PVC section bar erosion-resisting characteristics of preparing is thus high.
The preparation method of nano ceric oxide 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 ℃, add initiator, reaction;
(2) when reactor temperature starts to rise, open temperature lowering water cooling, when temperature rises to summit and starts to decline, in still, add nano ceric oxide;
(3) when temperature continues to drop to 60 ~ 65 ℃, close temperature lowering water, when temperature in the kettle drops to 45 ~ 48 ℃ naturally, blowing, dry, obtain powdery product.
Wherein:
In order to regulate better temperature and to make reaction more stable, polymerization single polymerization monomer described in step (1) divides two sections or multistage to add, and minutes two sections add fashionablely, 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 ceric oxide 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.
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) adopt nano ceric 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 graininess good fluidity, and the PVC section bar erosion-resisting characteristics of preparing is thus 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: 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 Sodium Persulfate, 15 kilograms of sodium laurylsulfonates, 5 kilograms of nano ceric oxides (particle diameter is 20 ± 5nm).
Preparation method: to the softening water that adds set amount in glassed steel reaction vessels, open and stir, 75 revs/min of mixing speed, add emulsifying agent, 480 kilograms of polymeric monomer composites, capping still, opens heating, when reactor temperature reaches 65 ℃, 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 approximately 78 ℃, no longer rise, and while starting to drop to 70 ℃, in still, add nano ceric oxide and 520 kilograms of two sections of monomer compositions, carry out second-stage reaction, in reaction, temperature is controlled at below 80 ℃.Reacted rear temperature and declined, when dropping to 63 ℃, closed temperature lowering water, when temperature in the kettle drops to 45 ℃ naturally, blowing, is dried and becomes pulverous nano ceric oxide impact modified acrylic ester family macromolecule polymer A.Take chloroform as solvent, at 25 ± 0.1 ℃ of temperature, measure, find that its limiting viscosity is 11.6, 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, 0.5 kilogram of ammonium persulphate, 15 kilograms of sodium lauryl sulphate, 10 kilograms of nano ceric oxides (particle diameter is 30 ± 5nm).
Preparation method: to the softening water that adds set amount in glassed steel reaction vessels, open and stir, 60 revs/min of mixing speed, add emulsifying agent, 700 kilograms of polymeric monomer composites, capping still, opens heating, when reactor temperature reaches 66 ℃, 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 approximately 77 ℃, no longer rise, and while starting to drop to 70 ℃, in still, add nano ceric oxide and 300 kilograms of two sections of monomer compositions, carry out second-stage reaction, in reaction, temperature is controlled at below 80 ℃.Reacted rear temperature and declined, when dropping to 65 ℃, closed temperature lowering water, when temperature in the kettle drops to 48 ℃ naturally, blowing, is dried and becomes pulverous nano ceric oxide impact modified acrylic ester family macromolecule polymer B.Take chloroform as solvent, at 25 ± 0.1 ℃ of temperature, measure, find that its limiting viscosity is 11.1, hereinafter to be referred as properties-correcting agent B.
Embodiment 3
Raw material: 1600 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 5 kilograms of Sodium Persulfates, 15 kilograms of Sodium dodecylbenzene sulfonatees, 20 kilograms of nano ceric oxides (particle diameter is 50 ± 5nm).
Preparation method: to the softening water that adds set amount in glassed steel reaction vessels, open and stir, 68 revs/min of mixing speed, add emulsifying agent, 300 kilograms of polymeric monomer composites, capping still, opens heating, when reactor temperature reaches 68 ℃, 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 approximately 78 ℃, no longer rise, and while starting to drop to 70 ℃, in still, add nano ceric oxide and 700 kilograms of two sections of monomer compositions, carry out second-stage reaction, in reaction, temperature is controlled at below 80 ℃.Reacted rear temperature and declined, when dropping to 60 ℃, closed temperature lowering water, when temperature in the kettle drops to 46 ℃ naturally, blowing, is dried and becomes pulverous nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance C.Take chloroform as solvent, at 25 ± 0.1 ℃ of temperature, measure, find that its limiting viscosity is 10.8, 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, 1 kilogram of Sodium Persulfate, 1 kilogram of OP-10,30 kilograms of nano ceric oxides (particle diameter is 80 ± 5nm).
Embodiment 4 preparation methods, as embodiment 1, obtain nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance D, take chloroform as solvent, at 25 ± 0.1 ℃ of temperature, measure, and find that its limiting viscosity is 10.4, hereinafter to be referred as properties-correcting agent D.
Embodiment 5
Raw material: 1500 kilograms of softening waters, 1000 kilograms of methyl methacrylates, 2 kilograms of Sodium Persulfates, 5 kilograms of sodium lauryl sulphate, 40 kilograms of nano ceric oxides (particle diameter is 100 ± 5nm).
Embodiment 5 preparation methods, as embodiment 1, obtain nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance E, take chloroform as solvent, at 25 ± 0.1 ℃ of temperature, measure, and find that its limiting viscosity is 10.0, hereinafter to be referred as properties-correcting agent E.
Embodiment 6
Raw material: 1500 kilograms of softening waters, 250 kilograms of methyl methacrylates, 750 kilograms of butyl acrylates, 3 kilograms of Sodium Persulfates, 36 kilograms of Sodium dodecylbenzene sulfonatees, 50 kilograms of nano ceric oxides (particle diameter is 50 ± 5nm).
Embodiment 6 preparation methods, as embodiment 1, obtain nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance F, take chloroform as solvent, at 25 ± 0.1 ℃ of temperature, measure, and find that its limiting viscosity is 9.6, hereinafter to be referred as properties-correcting agent F.
Comparative example 1
Raw material: 1500 kilograms of softening waters, 600 kilograms of methyl methacrylates, 400 kilograms of butyl acrylates, 1 kilogram of Sodium Persulfate, 15 kilograms of sodium laurylsulfonates.
In comparative example 1 preparation method, except plus nano cerium dioxide not, all the other,, as embodiment 1, obtain modification acrylate family macromolecule polymkeric substance M, take chloroform as solvent, at 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 ~ 6 and comparative example 1 are carried out to 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
Note: ★ more multilist shows that graininess mobility is better.
2, the mensuration of PVC goods erosion-resisting characteristics:
Base material formulation is as follows, and Ge Zu unit is kg:
Get 1kg modifier A and join in above base material formulation, make test material 1.;
Get 2kg modifier A and join in above base material formulation, make test material 2.;
Get 5kg modifier A and join in above base material formulation, make test material 3.;
Get 1kg properties-correcting agent M and join in above base material formulation, make test material I;
Get 2kg properties-correcting agent M and join in above base material formulation, make test material II;
Get 5kg properties-correcting agent M and join in above base material formulation, make test material III.
Above-mentioned each component is joined in high-speed mixer, open and stir, when temperature is elevated to 110 ℃, cooling blowing, when temperature is reduced to room temperature, is placed on double roller plastic-making device, at 190 ℃, open refining 4 minutes, pull into sheet material, then by the thickness requirement of test, at vulcanizing press, at 190 ℃, under the condition of 15MPa, compacting in flakes, obtain PVC sheet 1. ~ 3. with PVC sheet I ~ III, according to the requirement of GB/T1403, test its simple beam impact strength, 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 ℃ 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 ℃ of single notched Izod impact strength (KJ/m 2） | 3.48 | 3.91 | 4.72 |
From table 2 data analysis, the PVC section bar erosion-resisting characteristics that adopts nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance to prepare is obviously better than the PVC section bar of preparing with common properties-correcting agent.And under the similar condition of erosion-resisting characteristics, the polymkeric substance cost that this method is used.
Claims (1)
1. a preparation method for nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance, is characterized in that: comprise the following steps:
To the softening water that adds set amount in glassed steel reaction vessels, open and stir, 75 revs/min of mixing speed, add emulsifying agent, 480 kilograms of polymeric monomer composites, capping still, open heating, when reactor temperature reaches 65 ℃, 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 ℃, no longer rise, and while starting to drop to 70 ℃, in still, add nano ceric oxide and 520 kilograms of two sections of monomer compositions, carry out second-stage reaction, in reaction, temperature is controlled at below 80 ℃, having reacted rear temperature declines, when dropping to 63 ℃, close temperature lowering water, when temperature in the kettle drops to 45 ℃ naturally, blowing, be dried and become pulverous nano ceric oxide impact modified acrylic ester family macromolecule polymkeric substance,
Comprise following 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, initiator is 1 kilogram of Sodium Persulfate, emulsifying agent is 15 kilograms of sodium laurylsulfonates, 5 kilograms of nano ceric oxides, the particle diameter of nano ceric oxide is 20 ± 5nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210514074.8A CN102964507B (en) | 2012-12-05 | 2012-12-05 | Nano ceria impact resistant modified acrylate polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210514074.8A CN102964507B (en) | 2012-12-05 | 2012-12-05 | Nano ceria impact resistant modified acrylate polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102964507A CN102964507A (en) | 2013-03-13 |
| CN102964507B true CN102964507B (en) | 2014-10-29 |
Family
ID=47794962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210514074.8A Expired - Fee Related CN102964507B (en) | 2012-12-05 | 2012-12-05 | Nano ceria impact resistant modified acrylate polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102964507B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987115A (en) * | 2017-05-14 | 2017-07-28 | 合肥鼎鑫模具有限公司 | High-toughness wear-resistant automobile fixing piece mould and its manufacture method |
| CN108129598A (en) * | 2017-11-22 | 2018-06-08 | 内蒙古联丰稀土化工研究院有限公司 | The production method of acrylic rare earth modified PVC |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239548C (en) * | 1999-09-08 | 2006-02-01 | 巴斯福股份公司 | Method for producing aqueous dispersion of particles made up of polymerisate and fine inorganic solid material |
| CN103183767A (en) * | 2011-12-30 | 2013-07-03 | 山东世拓高分子材料股份有限公司 | Nano-ceria-modified acrylate linear high-molecular polymer and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161496A (en) * | 2008-01-09 | 2009-07-23 | Nippon Shokubai Co Ltd | Method for producing cosmetic |
-
2012
- 2012-12-05 CN CN201210514074.8A patent/CN102964507B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239548C (en) * | 1999-09-08 | 2006-02-01 | 巴斯福股份公司 | Method for producing aqueous dispersion of particles made up of polymerisate and fine inorganic solid material |
| CN103183767A (en) * | 2011-12-30 | 2013-07-03 | 山东世拓高分子材料股份有限公司 | Nano-ceria-modified acrylate linear high-molecular polymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘康强等.纳米CeO2的制备及其在PMMA中的分散.《中国稀土学报》.2011,第29卷(第6期),第737-742页. |
| 纳米CeO2的制备及其在PMMA中的分散;刘康强等;《中国稀土学报》;20111231;第29卷(第6期);第737-742页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102964507A (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102807721B (en) | Impact modifier for polymethyl methacrylate resin having excellent impact strength and transparency and method of preparing the same | |
| JP6413767B2 (en) | POLYMER, PROCESS FOR PRODUCING THE SAME, AND MOLDED BODY | |
| CN105418836A (en) | Preparation method of acrylate polymer/nanometer silicon dioxide composite particles for polycarbonate toughening | |
| CN105482342B (en) | Excellent vinyl chloride resin of cryogenic property and preparation method thereof | |
| EP3083727A1 (en) | Process for the preparation of polymers based on vinyl halides | |
| CN103130962B (en) | Chlorinated polyethylene rubber, butyl acrylate, acrylonitrile, N phenyl maleimide graft copolymer and preparation method thereof | |
| CN102964507B (en) | Nano ceria impact resistant modified acrylate polymer and preparation method thereof | |
| CN103788281A (en) | Core-shell structure processing agent for rigid polyvinyl chloride and synthetic method thereof | |
| CN104945763B (en) | The preparation method of acrylonitrile styrene acrylic ester toughened resin based on block copolymer | |
| CN102964506B (en) | Nano zinc dioxide impact-resistant modified acrylate polymer and preparation method thereof | |
| CN103012659B (en) | Nano-calcium-carbonate modified impact-resisting acrylate high-molecular polymer and method for preparing same | |
| KR101515269B1 (en) | Acrylic copolymer latex, and method for preparing thereof | |
| WO2006112192A1 (en) | (meth)acrylic polymer and vinyl chloride resin composition containing the same | |
| JP5131956B2 (en) | Thickener and method for producing the same | |
| CN102964510B (en) | Nano alumina impact resistant modified acrylate polymer and preparation method thereof | |
| CN102964509B (en) | Nano titania impact resistant modified acrylate polymer and preparation method thereof | |
| CN102964511B (en) | Nano barium sulfate impact resistant modified acrylate polymer and preparation method thereof | |
| CN102964508B (en) | Nano silica impact resistant modified acrylate polymer and preparation method thereof | |
| CN103183769B (en) | Nano-silicon dioxide modified acrylic ester class linear macromolecule polymkeric substance and method for making | |
| CN103183768B (en) | Nono calcium carbonate modified esters of acrylic acid linear macromolecule polymkeric substance and method for making | |
| CN103183770B (en) | Nano-titanium dioxide modified esters of acrylic acid linear macromolecule polymkeric substance and method for making | |
| WO2014019109A1 (en) | Processing modifier used for polyvinyl chloride pipe and pipe fitting | |
| CN103183767B (en) | Nano ceric oxide modification acrylate class linear macromolecule polymkeric substance and method for making | |
| CN101386655A (en) | High molecule dispersants for polychloroethylene synthesis, high molecule dispersants preparation method and applications | |
| US9845370B2 (en) | Method of preparing heat-resistant resin, heat-resistant resin and heat-resistant ABS resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANDONG SHITUO LIFENG CHEMICAL TECHNOLOGY CO., LT Free format text: FORMER OWNER: SHANDONG SHITUO HIGH MOLECULAR WEIGHT MATERIAL CO., LTD. Effective date: 20150812 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150812 Address after: West Grange village 271100 Shandong province Laiwu steel Lixin Street Office Patentee after: Shandong World Chemical Co., Ltd., Polytron Technologies Inc Address before: 256100 south Ling Road, Yiyuan Economic Development Zone, Zibo, Shandong Patentee before: Shandong Shituo High Molecular Weight Material Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141029 Termination date: 20151205 |
|
| EXPY | Termination of patent right or utility model |