CN101220122A - Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same - Google Patents
Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same Download PDFInfo
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- CN101220122A CN101220122A CNA2008100332410A CN200810033241A CN101220122A CN 101220122 A CN101220122 A CN 101220122A CN A2008100332410 A CNA2008100332410 A CN A2008100332410A CN 200810033241 A CN200810033241 A CN 200810033241A CN 101220122 A CN101220122 A CN 101220122A
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- calcium carbonate
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Abstract
The invention provides a plastic toughening agent that contains nano calcium carbonate and polymer and the preparation method thereof. The invention designs a polymer with high molecular weight and uses the polymer in the surface treatment of calcium carbonate to prepare and obtain the plastic toughening agent. The toughening agent of the invention can serve as the filling of plastic products. Since the polymer with high molecular weight is contained, the heat resistance, wear resistance, size stability, impact resistance, rigidity, severity and workability of the products are enhanced and unit cost of plastic products is reduced.
Description
Technical field
The present invention relates to a kind of plastics toughening agent that contains nano-calcium carbonate and polymkeric substance and preparation method thereof.
Background technology
Lime carbonate can improve thermotolerance, wear resistance, dimensional stability, shock resistance, hardness, rigidity and the workability of goods as the filler of product of rubber and plastic, and reduces the unit cost of product of rubber and plastic.Usually, calcium carbonate product has stronger alkalescence, and is hydrophilic oleophobic property, and is poor with the affinity of polymkeric substance, and the dispersion in polymkeric substance is difficulty comparatively.Along with the increase of calcium carbonate-filled amount, these shortcomings are more obvious, even make goods forfeiture use value.In recent years, nanotechnology is risen, and nano-calcium carbonate and calcium carbonate superfine powder are widely used in every field.
But because the calcium carbonate superfine powder particle diameter diminishes, the surface atom number increases, and surface energy increases, and adsorption strengthens, and is tending towards mutual reunion between particle, thereby causes particle can not disperse well in polymeric matrix; The general character of the hydrophilic oleophobic of lime carbonate makes itself and polymkeric substance easily form boundary defect in addition.For improve the dispersed of nano-calcium carbonate and calcium carbonate superfine powder and with the polymer phase capacitive, bring into play its toughness reinforcing, reinforcing function, be necessary nanometer and calcium carbonate superfine powder are carried out surface modification, bring into play its nano effect, make it become a kind of functional modification material, thereby widen its Application Areas.
The research of surface-modifying agent is one of powder-modified key areas, also is the new focus of area researches such as powder deep processing and advanced composite material.In fact the active modification of lime carbonate is exactly to select specific surface-modifying agent, and the calcium carbonate granule surface is coated processing, makes it to become the function packing material.The kind of surface-modifying agent and modified technique will directly influence surface modification effect.
Commonly used surface-modifying agent and method of modifying have: organism properties-correcting agent, mineral-modified dose, coupling agent, polymer modifiers, Cement Composite Treated by Plasma and radiation treatment etc.
Properties-correcting agent the absorption of Paris white surface, coating, film forming or with surface mass generation chemical reaction, all can realize calcium carbonate modified purpose.The method that is used for surface modification at present mainly contains surface chemical reaction modification, the modification of precipitation chemical reaction, surface coating modification, microemulsion modification, high energy surface modification etc.Will utilize surface-modifying agent in the surface chemical reaction modified calcium carbonate process, surface-modifying agent commonly used has coupling agents such as titanic acid ester, aluminic acid ester, phosphoric acid ester, lipid acid tensio-active agents such as (salt) and inorganics etc.The surface modification technology of lime carbonate has dry method and wet method.The modification of lime carbonate dry method be with exsiccant calcium carbonate powder and surface-modifying agent according to certain proportioning dispersing and mixing in surface modification equipment, the control certain temperature is carried out the technology of calcium carbonate surface modifying.
Wet-process modified being meant of lime carbonate added surface-modifying agent and auxiliary agent in the lime carbonate suspension liquid of certain solid-to-liquid ratio, carry out the technology of surface modification under the control certain temperature.
Chinese patent 200410028166.0 discloses a kind of preparation method of modified nano calcium carbonate, be in nano-calcium carbonate or stearic acid modified nano-calcium carbonate dry powder, to add Resorcinol or Resorcinol donor and methylene radical donor, make modified nano calcium carbonate.Perhaps, in nano-calcium carbonate or stearic acid modified nano-calcium carbonate dry powder, add Resorcinol and vulkacit H complex compound (RH), make modified nano calcium carbonate.The modified nano calcium carbonate surface that obtains has coated one deck Resorcinol and vulkacit H, and produces firm combination by modes such as hydrogen bonds, can chemistry or physical bond take place with polymeric matrix, thereby strengthens its interface combination.
Disclose a kind of surface treatment method that improves hydrophobicity of Nano particles of calcium carbonate in the Chinese patent 02121034.9, adopted acrylic acid esters co-polymer emulsion that letex polymerization obtains under stirring condition, the nano-calcium carbonate slurries to be handled and realize improvement hydrophobicity of Nano particles of calcium carbonate as surface-modifying agent.
Chinese patent 200510023580.7 discloses a kind of method of modifying of nano-calcium carbonate, is the activation method of nano-calcium carbonate emulsion specifically.Adopt Gemini tensio-active agent bisphosphate salt as properties-correcting agent, the nano-calcium carbonate emulsion that Carbonization Preparation is obtained coats activation treatment, and its preparation method is at first nano-calcium carbonate to be made into emulsion, adds above-mentioned surface-modifying agent, stirs.To discard filtrate through the nano-calcium carbonate emulsion filtered while hot after the above-mentioned processing at last, drying is pulverized, and sieves and promptly gets the active nano-calcium carbonate finished product.
Above-mentioned prior art only is that activation treatment is carried out on the surface of nano-calcium carbonate, to improving the dispersiveness of nano-calcium carbonate in polarity plastics (as PVC) certain effect is arranged.The molecular weight of used treatment agent is less, produces negative influence to plastic toughening with to the aspects such as resistance to impact shock of plastics.
Summary of the invention
The purpose of this invention is to provide a kind of plastics toughening agent that contains nano-calcium carbonate and polymkeric substance and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
Thinking of the present invention is, designs a kind of high molecular weight polymers, and this polymkeric substance is suitable for the calcium carbonate wet-process surface treatment, and the plastics toughening agent for preparing has the effect to plastic toughening.
Method of the present invention comprises the steps:
With pH is the organic solvent that contains polymkeric substance of 7-10, adds the nano-calcium carbonate calcium contents and is in the waterborne suspension of heat of 0.8-2.0mol/L, stirs 1-3 hour, then from collecting said toughner;
The temperature of the waterborne suspension of heat is 40-100 ℃, preferably at 65-95 ℃;
Described pH can adopt ammoniacal liquor, and the NaOH aqueous solution or the KOH aqueous solution are regulated;
Organic solvent is selected from one or more in propyl carbinol, Virahol, 2-methyl cellosolve, propylene glycol monomethyl ether, methyl phenyl ketone or the butanone, in the organic solvent, the weight concentration of polymkeric substance is 60～90%, the consumption of polymkeric substance is the 1-20% (wt) of nano-calcium carbonate quality, preferably 3-15% (wt);
The particle diameter of said nano-calcium carbonate is 10～100 nanometers, especially 15～80 nanometers, preferably 20～40 nanometers;
Said stirring can be adopted modes such as common stirring shearing, emulsification pump shearing or colloidal mill shearing;
Said polymkeric substance is to adopt the free radical polymerisation process preparation with the raw material of following weight part:
Soft monomer: 50-80 part
Hard monomer: 10-25 part
Wetting ability function monomer: 10-25 part
Initiator: 0.1-3 part
Solvent: 20-60 part
Said soft monomer is an ethyl propenoate, n-butyl acrylate, isobutyl acrylate, isodecyl methacrylate, one or more in vinylformic acid n-octyl or the n octyl methacrylate;
Described hard monomer is a vinylbenzene, one or more in vinyl-acetic ester or the methyl methacrylate;
Described wetting ability function monomer is one or more in hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid, vinylformic acid or the MALEIC ANHYDRIDE;
Said initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or the dibenzoyl peroxide;
Said solvent is one or more mixtures in propyl carbinol, Virahol, 2-methyl cellosolve, propylene glycol monomethyl ether, methyl phenyl ketone or the butanone;
Its preparation method comprises the steps:
Soft monomer, hard monomer and wetting ability functional monomer and initiator are added drop-wise in 1h-4h in the solvent according to above-mentioned weight proportion, and control reaction temperature is at 60-100 ℃, and polymerization time is 4-10 hour, obtains polymers soln;
The polymkeric substance principal character is the structure with soft section, hard section and wetting ability functional group, and its molecular weight is 20000～100000.
Toughner of the present invention, can be as the filler of product of rubber and plastic, owing to contain the polymkeric substance of higher molecular weight, can improve thermotolerance, wear resistance, dimensional stability, shock resistance, hardness, rigidity and the workability of goods, and reduce the unit cost of product of rubber and plastic.
Embodiment
Below in conjunction with embodiment the present invention is further described.
The molecular weight gel chromatography of polymkeric substance.The modified nano calcium carbonate that obtains the most at last carries out Determination of oil-absorbed value.Oil-absorption(number) characterizes with the gram number of the DOP (dibutyl phthalate) that the 100g modified nano calcium carbonate consumes.
Embodiment 1
1. the preparation of the solution polymerization of nano-calcium carbonate surface-modifying agent (following is weight part):
(1) n-butyl acrylate 60
(2) vinylbenzene 10
(3) hydroxyethyl methylacrylate 15
(4) vinylformic acid 15
(5) Diisopropyl azodicarboxylate 0.1
(6) butanone 40
Polymerization single polymerization monomer and initiator Diisopropyl azodicarboxylate are added drop-wise in the solvent butanone, and temperature is controlled at 85 ℃, and polymerization time is 8 hours, obtains the polyacrylate solution polymerisate, the molecular weight Mw=34208 of resulting polymers.
2. nano-calcium carbonate surface coating modification:
Polyacrylic ester is regulated pH=10 with ammonia soln, join temperature then and be in 80 ℃ of waterborne suspensions that contain nano-calcium carbonate, shear conditions was handled 80 minutes down.Wherein, the nano-calcium carbonate size is 38nm, and the nano-calcium carbonate calcium contents is 1.2mol/L in the waterborne suspension; The consumption of polyacrylate solution is 6% of nano-calcium carbonate quality according to polymer solids Mass Calculation in this solution, the product that filter, drying obtains the present invention's explanation, and recording oil-absorption(number) is 22.
Embodiment 2
1. the preparation of the solution polymerization of nano-calcium carbonate surface-modifying agent (following is weight part):
(1) the vinylformic acid n-octyl 80
(2) methyl methacrylate 10
(3) methacrylic acid 10
(4) dibenzoyl peroxide 3
(5) Virahol 20
Polymerization single polymerization monomer and initiator dibenzoyl peroxide are added drop-wise in the solvent Virahol, and temperature is controlled at about 85 ℃, and polymerization time is 8 hours, obtains the polyacrylate solution polymerisate, the molecular weight Mw=32860 of polymkeric substance.
2. nano-calcium carbonate surface coating modification:
Polyacrylic ester is regulated pH=7 with aqueous sodium hydroxide solution, join temperature then and be in 85 ℃ the waterborne suspension that contains nano-calcium carbonate, shear conditions was handled 90 minutes down.Wherein, the nano-calcium carbonate size is 65nm, and the nano-calcium carbonate calcium contents is 1.6mol/L in the waterborne suspension; The consumption of polyacrylate solution is 3% of nano-calcium carbonate quality according to polymer solids Mass Calculation in this solution.Filtration, drying obtain the product that the present invention illustrates, recording its oil-absorption(number) is 24.
Embodiment 3
1. the solution polymerization of nano-calcium carbonate surface-modifying agent (following is weight part):
(1) n-butyl acrylate 50
(2) vinylbenzene 10
(3) methyl methacrylate 15
(4) MALEIC ANHYDRIDE 10
(5) vinylformic acid 15
(6) Diisopropyl azodicarboxylate 1
(7) Virahol 40
Polymerization single polymerization monomer and initiator Diisopropyl azodicarboxylate are added drop-wise in the solvent Virahol, and temperature is controlled at about 85 ℃, and polymerization time is 8 hours, obtains the polyacrylate solution polymerisate, the molecular weight Mw=32375 of polymkeric substance.
2. nano-calcium carbonate surface coating modification:
Polyacrylic ester is regulated pH=8 with aqueous sodium hydroxide solution, join temperature then and be in 90 ℃ the waterborne suspension that contains nano-calcium carbonate, shear conditions was handled 75 minutes down.Wherein, the nano-calcium carbonate size is 55nm, and the nano-calcium carbonate calcium contents is 1.2mol/L in the waterborne suspension; The consumption of polyacrylate solution is 5% of nano-calcium carbonate quality according to polymer solids Mass Calculation in this solution.Filtration, drying obtain the product that the present invention illustrates, recording its oil-absorption(number) is 24.
Embodiment 4
1. the preparation of the solution polymerization of nano-calcium carbonate surface-modifying agent (following is weight part)
(1) n-butyl acrylate 60
(2) vinylbenzene 10
(3) methyl methacrylate 10
(4) vinylformic acid 20
(5) Diisopropyl azodicarboxylate 1
(6) butanone 60
Polymerization single polymerization monomer and initiator Diisopropyl azodicarboxylate are added drop-wise in the solvent butanone, and temperature is controlled at about 85 ℃, and polymerization time is 8 hours, obtains the polyacrylate solution polymerisate, the molecular weight Mw=35130 of polymkeric substance.
2. nano-calcium carbonate surface coating modification:
Polyacrylic ester is regulated pH=9 with potassium hydroxide aqueous solution, join temperature then and be in 75 ℃ the waterborne suspension that contains nano-calcium carbonate, shear conditions was handled 80 minutes down.Wherein, the nano-calcium carbonate size is 38nm, and the nano-calcium carbonate calcium contents is 1.7mol/L in the waterborne suspension; The consumption of polyacrylate solution is 3% of nano-calcium carbonate quality according to polymer solids Mass Calculation in this solution.Filtration, drying obtain the product that the present invention illustrates, recording its oil-absorption(number) is 23.
Embodiment 5
1. the preparation of the solution polymerization of nano-calcium carbonate surface-modifying agent (following is weight part):
(1) n-butyl acrylate 70
(3) methyl methacrylate 10
(5) vinylformic acid 20
(6) dibenzoyl peroxide 1
(7) butanone 40
Polymerization single polymerization monomer and initiator dibenzoyl peroxide are added drop-wise in the solvent butanone, and temperature is controlled at about 85 ℃, and polymerization time is 8 hours, obtains the polyacrylate solution polymerisate, the molecular weight Mw=35205 of polymkeric substance.
2. nano-calcium carbonate surface coating modification:
Polyacrylic ester is regulated pH=7-10 with ammonia soln, join temperature then and be in 80 ℃ the waterborne suspension that contains nano-calcium carbonate, shear conditions was handled 65 minutes down.Wherein, the nano-calcium carbonate size is 35nm, and the nano-calcium carbonate calcium contents is 1.2mol/L in the waterborne suspension; The consumption of polyacrylate solution is 10% of nano-calcium carbonate quality according to polymer solids Mass Calculation in this solution.Filtration, drying obtain the product that the present invention illustrates, recording its oil-absorption(number) is 22.
Claims (10)
1. a polymkeric substance is characterized in that, is to adopt the free radical polymerisation process preparation with the raw material of following weight part:
Soft monomer: 50-80 part
Hard monomer: 10-25 part
Wetting ability function monomer: 10-25 part
Initiator: 0.1-3 part
Solvent: 20-60 part
Said soft monomer is an ethyl propenoate, n-butyl acrylate, isobutyl acrylate, isodecyl methacrylate, one or more in vinylformic acid n-octyl or the n octyl methacrylate;
Described hard monomer is a vinylbenzene, one or more in vinyl-acetic ester or the methyl methacrylate;
Described wetting ability function monomer is one or more in hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid, vinylformic acid or the MALEIC ANHYDRIDE;
Said initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or the dibenzoyl peroxide;
Said solvent is one or more mixtures in propyl carbinol, Virahol, 2-methyl cellosolve, propylene glycol monomethyl ether, methyl phenyl ketone or the butanone.
2. polymkeric substance according to claim 1, it is characterized in that, the preparation method comprises the steps: among 1h-4hs to be added drop-wise in solvent according to above-mentioned weight proportion soft monomer, hard monomer and wetting ability functional monomer and initiator, control reaction temperature is at 60-100 ℃, polymerization time is 4-10h, obtains polymers soln.
3. polymkeric substance according to claim 1 and 2 is characterized in that, polymer features is the structure with soft section, hard section and wetting ability functional group, and molecular weight is 20000～100000.
4. preparation method who contains the plastics toughening agent of nano-calcium carbonate and polymkeric substance, it is characterized in that, comprise the steps: with pH to be the organic solvent that contains each described polymkeric substance of claim 1～3 of 7-10, add the nano-calcium carbonate calcium contents and be in the waterborne suspension of heat of 0.8-2.0mol/L, stirred 1-3 hour, and collected said toughner then.
5. method according to claim 4 is characterized in that, the temperature of the waterborne suspension of heat is 40-100 ℃.
6. method according to claim 4 is characterized in that described pH can adopt ammoniacal liquor, and the NaOH aqueous solution or the KOH aqueous solution are regulated.
7. method according to claim 4, it is characterized in that organic solvent is selected from one or more in propyl carbinol, Virahol, 2-methyl cellosolve, propylene glycol monomethyl ether, methyl phenyl ketone or the butanone, in the organic solvent, the weight concentration of polymkeric substance is 60～90%, and the consumption of polymkeric substance is the 1-20% (wt) of nano-calcium carbonate quality.
8. according to each described method of claim 4～7, the particle diameter that it is characterized in that said nano-calcium carbonate is 10～100 nanometers.
9. method according to claim 4 is characterized in that said stirring employing stirring shearing, emulsification pump shearing or colloidal mill shearing etc.
10. adopt the plastics toughening agent of each described method preparation of claim 4～9.
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| CN 200810033241 CN101220122B (en) | 2008-01-30 | 2008-01-30 | Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same |
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| CN 200810033241 CN101220122B (en) | 2008-01-30 | 2008-01-30 | Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same |
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| CN101220122A true CN101220122A (en) | 2008-07-16 |
| CN101220122B CN101220122B (en) | 2010-06-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421142A (en) * | 2013-07-18 | 2013-12-04 | 贺州学院 | Ground calcium carbonate powder surface modification method |
| CN104725543A (en) * | 2015-03-18 | 2015-06-24 | 阜阳市诗雅涤新材料科技有限公司 | Ultrahigh-acid value acrylate resin as well as synthesis method and application of resin |
| CN111073174A (en) * | 2019-12-25 | 2020-04-28 | 广东祺龙科技有限公司 | Odorless antistatic PVC composite material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394928A (en) * | 2001-07-06 | 2003-02-05 | 中国科学院化学研究所 | Preparation method of UV-light solidified pressure-sensitive adhesive |
| CN1228357C (en) * | 2002-12-11 | 2005-11-23 | 中国石油化工股份有限公司 | Polymerization process of random styrene-cis-butenedioic anhydride copolymer |
| WO2007008971A1 (en) * | 2005-07-11 | 2007-01-18 | Henkel Corporation | Toughened cyanoacrylate compositions |
| CN100430424C (en) * | 2006-10-24 | 2008-11-05 | 河北工业大学 | Process for preparing acrylate resin for powder paint |
-
2008
- 2008-01-30 CN CN 200810033241 patent/CN101220122B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421142A (en) * | 2013-07-18 | 2013-12-04 | 贺州学院 | Ground calcium carbonate powder surface modification method |
| CN103421142B (en) * | 2013-07-18 | 2015-11-25 | 贺州学院 | A kind of Ground calcium carbonate powder surface modification method |
| CN104725543A (en) * | 2015-03-18 | 2015-06-24 | 阜阳市诗雅涤新材料科技有限公司 | Ultrahigh-acid value acrylate resin as well as synthesis method and application of resin |
| CN111073174A (en) * | 2019-12-25 | 2020-04-28 | 广东祺龙科技有限公司 | Odorless antistatic PVC composite material and preparation method thereof |
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| CN101220122B (en) | 2010-06-02 |
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Application publication date: 20080716 Assignee: Jiande calcium carbonate Research Center Co Ltd Assignor: Huaming High Technology (Group) Co., Ltd., Shanghai Contract record no.: 2014310000006 Denomination of invention: Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same Granted publication date: 20100602 License type: Common License Record date: 20140121 |
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