CN1330714C - Method of preparing nano-silicone dioxide capable of inducing poly vinyl chloide crystallization - Google Patents
Method of preparing nano-silicone dioxide capable of inducing poly vinyl chloide crystallization Download PDFInfo
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- CN1330714C CN1330714C CNB2005100181703A CN200510018170A CN1330714C CN 1330714 C CN1330714 C CN 1330714C CN B2005100181703 A CNB2005100181703 A CN B2005100181703A CN 200510018170 A CN200510018170 A CN 200510018170A CN 1330714 C CN1330714 C CN 1330714C
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Abstract
The present invention provides a preparation method for a processing auxiliary agent for enhancing the strength and the toughness of a PVC material, particularly a preparation method for a PVC modification auxiliary agent for a modification nanometer inorganic particle class. The present invention uses the traditional crystal enhancement technique to research a modification method for a novel PVC strength and toughness increasing agent in order to simultaneously enhance the strength and the toughness of hard PVC. The induced crystal matter of modification nanometer silicon dioxide is used in the processing process of the hard PVC by the method, and PVC molecules form uniform microcrystals in a processing and shaping process. The crystallinity of PVC is markedly enhanced, the tensile strength of the PVC is enhanced 12 to 50%, and the impact resistant strength of the PVC is enhanced 20 to 65%. The cost of the modification nanometer silicon dioxide prepared by the present invention is low, and the technical defects of the processing and the modification of a PVC material at present are overcome. The present invention has wide application prospect.
Description
Technical field
The present invention relates to preparation method of nano silicon dioxide, particularly the preparation of the nano silicon of surface aggregate thing coating modification.
Background technology
Rigid polyvinyl chloride (PVC) is widely used: polyvinyl chloride building plastic tubing and section bar can substitute timber and metal as the maximum kind of new chemical building materials, and have excellent energy-saving effect.
Because the toughness of hard PVC is relatively poor, need carry out impact-resistant modified to it.Method to the hard PVC modification mainly contains at present: elastic body toughening PVC, rigid particles toughening PVC and nanometer particle-modified PVC etc.As: Liu Minjiang people such as (seeing Chinese plastic engineering second modifying plastics academic meeting paper of association [C] .1998.) finds: with the increase of ACR add-on, the hard PVC material shock strength progressively rises, especially in 5～10 parts of scopes, the variation of shock strength is the fastest, and reach maximum substantially 10 parts the time, but the adding of ACR descends HPVC tensile strength, hardness to some extent.This is to use maximum method of modifying at present.People such as Yang Wenjun (see plastics (J), 1992, (1): 7-10,51.) add PMMA, PS, AS among PVC/MBS, PVC/CPE, the PVC/NBR to, study them to pre-toughened matrix system Effect on Performance.In general, PMMA (3～6 parts) is better to the PVC/MBS modified effect, and PS (3 parts) is to PVC/CPE 100/10) the system improved performance is effective, and AS is little to PVC/NBR system modified effect, not as the PVC/MBS system.People such as Tian Manhong (see polyvinyl chloride (J), 2003, (1): 26-29,32) adopt methods such as ultrasonic wave, vibration to nanometer SiO
2Particle carries out surface treatment, and the method by melt blending has prepared PVC/SiO
2Nano composite material.Studied enhancing, the toughening effect of nanoparticle to PVC.
But the toughening modifying method that uses can be sacrificed some intensity when improving toughness of material at present.Seldom there is a kind of method to play and improves hard PVC intensity and flexible effect simultaneously.
Nearly all metallic substance, part stupalith and a lot of macromolecular material can reach by the crystallization enhancing and strengthen toughness reinforcing purpose, for example amorphous polypropylene material does not almost have intensity, and the isotatic polypropylene of highly crystalline has good mechanical mechanics property.But for polyvinyl chloride, (140 ℃ begin to decompose because the PVC decomposition temperature is low, the common process process all need add stablizer), its crystalline melt temperature height (210 ℃), surpassed the violent decomposition temperature (200 ℃) after PVC adds stablizer, cause the forming process difficulty, so conventional P VC complete processing wishes to avoid the crystallization of PVC.
Summary of the invention
The objective of the invention is defective, selected a kind of intensity and flexible preparation method that can improve hard PVC simultaneously at prior art.The present invention utilizes traditional crystallization enhancement techniques, study a kind of novel PVC and strengthened toughness reinforcing method of modifying, this method is used for modified manometer silicon dioxide induced crystallization material the course of processing of hard PVC, make the PVC molecule generate uniform microcrystal in the machine-shaping later stage, significantly improve the degree of crystallinity of PVC, and making the tensile strength of PVC improve 12～50%, resistance to impact shock improves 20～65%.
The concrete technical scheme of the present invention is:
Adopting median size is the nano silicon of 10～50nm, with properties-correcting agent nano silicon is done surperficial oleophylic processing, and properties-correcting agent can be silane resin acceptor kh-550 or KH-570, and its consumption is 0.5～2.5% of silicon-dioxide by weight percentage.The method of surface oleophylic processing is: it is 0.5～2.5% aqueous isopropanol that KH-550 or KH-570 are configured to mass concentration, mix in the aqueous isopropanol adding nano silicon with properties-correcting agent, in 50～60 ℃ of heating 2～4 hours, get standby A component.
, will slowly add in the standby A component with the isopyknic polymers soln B of standby A component component under the condition to standby A component dispersed with stirring in room temperature, the B component adds the back fully and continues to stir 2 hours.B component institute dissolved polymers is separated out in this process and is coated on nano-silica surface.After stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent all volatilize the exsiccant modified manometer silicon dioxide.This modified manometer silicon dioxide can be used as induces PVC crystalline crystal seed.
Wherein, standby B component is following B
1, B
2, B
3, B
4In any one:
1. with number-average molecular weight be 100,000 HDPE to be dissolved in boiling range be in 60～90 ℃ the sherwood oil, be configured to mass concentration and be 0.5～2% HDPE petroleum ether solution, standby B
1Component;
2. with number-average molecular weight be 100,000 isotactic PP to be dissolved in boiling range be in 60～90 ℃ the sherwood oil, be configured to mass concentration and be 0.5～2% isotactic PP petroleum ether solution, standby B
2Component;
3. be that 10,000 nylon 1010 is dissolved in the acetone with number-average molecular weight, be configured to mass concentration and be 0.5～2% nylon 1010 acetone soln, standby B
3Component;
4. be that 10,000 poly(propylene oxide) is dissolved in the ethyl acetate with number-average molecular weight, be configured to mass concentration and be 0.5～2% poly(propylene oxide) ethyl acetate solution, standby B
4Component.
The modified manometer silicon dioxide that with mass ratio is 1: 100～10: 100 mixes with polyvinyl chloride resin, and then add other processing aids, the kind of other processing aids is identical with traditional hard PVC processing formula with consumption, after mixing, generate the PVC crystallite by traditional hard PVC complete processing, improve the degree of crystallinity of PVC.
The induced PVC crystalline nano silicon of the present invention's preparation can improve the strength and toughness of PVC material by inducing the PVC crystallization.The modified manometer silicon dioxide cost of this method preparation is lower, and it is obvious that the PVC material is strengthened toughening effect, has overcome the technological deficiency of present PVC materials processing modification, has broad application prospects.
Specific embodiments
The present invention is further described below in conjunction with embodiment:
Embodiment 1: adopting median size is the nano silicon of 10nm, with silane resin acceptor kh-550 nano silicon is done surperficial oleophylic processing, and its consumption is 2.5% of a silicon-dioxide.The method of surface oleophylic processing is: KH-550 is configured to 2.5% aqueous isopropanol, the aqueous isopropanol of properties-correcting agent is added in the nano silicon mixes, in 50 ℃ of heating 4 hours, standby A component.With number-average molecular weight be 100,000 HDPE to be dissolved in boiling range be in 60～90 ℃ the sherwood oil, be configured to mass concentration and be 2% HDPE petroleum ether solution, standby B
1Component.In room temperature under condition to standby A component dispersed with stirring, will with the isopyknic B of standby A component
1Component slowly adds in the standby A component, B
1Component adds the back fully and continues to stir 2 hours.B
1Component institute dissolved polymers is separated out in this process and is coated on nano-silica surface.After stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent all volatilize the exsiccant modified manometer silicon dioxide.To be that 5% modified manometer silicon dioxide is used for the processing of hard PVC pipe with the polyvinyl chloride resin mass ratio, improved the degree of crystallinity of PVC, obtain high performance pvc pipe material, compare with the hard PVC pipe that does not add modified manometer silicon dioxide processing, its tensile strength has improved 15%, and resistance to impact shock has improved 20%.
Embodiment 2: adopting median size is the nano silicon of 30nm, with silane resin acceptor kh-550 nano silicon is done surperficial oleophylic processing, and its consumption is 1.5% of a silicon-dioxide.The method of surface oleophylic processing is: KH-550 is configured to 1.5% aqueous isopropanol, the aqueous isopropanol of properties-correcting agent is added in the nano silicon mixes, in 50 ℃ of heating 4 hours, standby A component.With number-average molecular weight be 100,000 isotactic PP to be dissolved in boiling range be in 60～90 ℃ the sherwood oil, be configured to mass concentration and be 1% isotactic PP petroleum ether solution, standby B
2Component.In room temperature under condition to standby A component dispersed with stirring, will with the isopyknic B of standby A component
2Component slowly adds in the standby A component, B
2Component adds the back fully and continues to stir 2 hours.B
2Component institute dissolved polymers is separated out in this process and is coated on nano-silica surface.After stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent all volatilize the exsiccant modified manometer silicon dioxide.To be that 5% modified manometer silicon dioxide is used for the processing of hard PVC pipe with the polyvinyl chloride resin mass ratio, improved the degree of crystallinity of PVC, obtain high performance pvc pipe material, compare with the hard PVC pipe that does not add modified manometer silicon dioxide processing, its tensile strength has improved 20%, and resistance to impact shock has improved 30%.
Embodiment 3: adopting median size is the nano silicon of 50nm, with silane resin acceptor kh-550 nano silicon is done surperficial oleophylic processing, and its consumption is 0.5% of a silicon-dioxide.The method of surface oleophylic processing is: KH-550 is configured to 0.5% aqueous isopropanol, the aqueous isopropanol of properties-correcting agent is added in the nano silicon mixes, in 50 ℃ of heating 4 hours, standby A component.With number-average molecular weight be 100,000 isotactic PP to be dissolved in boiling range be in 60～90 ℃ the sherwood oil, be configured to mass concentration and be 0.5% isotactic PP petroleum ether solution, standby B
2Component.In room temperature under condition to standby A component dispersed with stirring, will with the isopyknic B of standby A component
2Component slowly adds in the standby A component, B
2Component adds the back fully and continues to stir 2 hours.B
2Component institute dissolved polymers is separated out in this process and is coated on nano-silica surface.After stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent all volatilize the exsiccant modified manometer silicon dioxide.To be that 5% modified manometer silicon dioxide is used for the processing of hard PVC pipe with the polyvinyl chloride resin mass ratio, improved the degree of crystallinity of PVC, obtain high performance pvc pipe material, compare with the hard PVC pipe that does not add modified manometer silicon dioxide processing, its tensile strength has improved 12%, and resistance to impact shock has improved 25%.
Embodiment 4: adopting median size is the nano silicon of 30nm, with silane resin acceptor kh-550 nano silicon is done surperficial oleophylic processing, and its consumption is 1.5% of a silicon-dioxide.The method of surface oleophylic processing is: KH-550 is configured to 1.5% aqueous isopropanol, the aqueous isopropanol of properties-correcting agent is added in the nano silicon mixes, in 50 ℃ of heating 4 hours, standby A component.With number-average molecular weight is that 10,000 nylon 1010 is dissolved in the acetone, be configured to mass concentration and be 1% nylon 1010 acetone soln, standby B
3Component.In room temperature under condition to standby A component dispersed with stirring, will with the isopyknic B of standby A component
3Component slowly adds in the standby A component, B
3Component adds the back fully and continues to stir 2 hours.B
3Component institute dissolved polymers is separated out in this process and is coated on nano-silica surface.After stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent all volatilize the exsiccant modified manometer silicon dioxide.To be that 5% modified manometer silicon dioxide is used for the processing of hard PVC pipe with the polyvinyl chloride resin mass ratio, improved the degree of crystallinity of PVC, obtain high performance pvc pipe material, compare with the hard PVC pipe that does not add modified manometer silicon dioxide processing, its tensile strength has improved 45%, and resistance to impact shock has improved 60%.
Embodiment 5: adopting median size is the nano silicon of 30nm, with silane resin acceptor kh-550 nano silicon is done surperficial oleophylic processing, and its consumption is 1.5% of a silicon-dioxide.The method of surface oleophylic processing is: KH-550 is configured to 1.5% aqueous isopropanol, the aqueous isopropanol of properties-correcting agent is added in the nano silicon mixes, in 50 ℃ of heating 4 hours, standby A component.With number-average molecular weight is that 10,000 nylon 1010 is dissolved in the acetone, be configured to mass concentration and be 1% nylon 1010 acetone soln, standby B
3Component.In room temperature under condition to standby A component dispersed with stirring, will with the isopyknic B of standby A component
3Component slowly adds in the standby A component, B
3Component adds the back fully and continues to stir 2 hours.B
3Component institute dissolved polymers is separated out in this process and is coated on nano-silica surface.After stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent all volatilize the exsiccant modified manometer silicon dioxide.To be that 10% modified manometer silicon dioxide is used for the processing of hard PVC pipe with the polyvinyl chloride resin mass ratio, improved the degree of crystallinity of PVC, obtain high performance pvc pipe material, compare with the hard PVC pipe that does not add modified manometer silicon dioxide processing, its tensile strength has improved 50%, and resistance to impact shock has improved 30%.
Embodiment 6: adopting median size is the nano silicon of 30nm, with silane coupling agent KH-570 nano silicon is done surperficial oleophylic processing, and its consumption is 1.5% of a silicon-dioxide.The method of surface oleophylic processing is: KH-570 is configured to 1.5% aqueous isopropanol, the aqueous isopropanol of properties-correcting agent is added in the nano silicon mixes, in 60 ℃ of heating 2 hours, standby A component.With number-average molecular weight is that 10,000 poly(propylene oxide) is dissolved in the ethyl acetate, be configured to mass concentration and be 1% poly(propylene oxide) ethyl acetate solution, standby B
4Component.In room temperature under condition to standby A component dispersed with stirring, will with the isopyknic B of standby A component
4Component slowly adds in the standby A component, B
4Component adds the back fully and continues to stir 2 hours.B
4Component institute dissolved polymers is separated out in this process and is coated on nano-silica surface.After stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent all volatilize the exsiccant modified manometer silicon dioxide.To be that 5% modified manometer silicon dioxide is used for the processing of hard PVC pipe with the polyvinyl chloride resin mass ratio, improved the degree of crystallinity of PVC, obtain high performance pvc pipe material, compare with the hard PVC pipe that does not add modified manometer silicon dioxide processing, its tensile strength has improved 30%, and resistance to impact shock has improved 65%.
Claims (2)
1, but a kind of method for preparing nano silica of inducing poly vinyl chloide crystallization, it is characterized in that adopting median size is the nano silicon of 10～50nm, with properties-correcting agent nano silicon is done surperficial oleophylic processing, properties-correcting agent is a kind of among silane resin acceptor kh-550 and the KH-570, its consumption is 0.5～2.5% of silicon-dioxide by weight percentage, the method of surface oleophylic processing is: it is 0.5～2.5% aqueous isopropanol that KH-550 or KH-570 are configured to mass concentration, mix in the aqueous isopropanol adding nano silicon with properties-correcting agent, in 50～60 ℃ of heating 2～4 hours, get standby A component, with HDPE, isotactic PP, nylon 1010 or poly(propylene oxide) be dissolved in nonpolar or weakly polar organic solvent in, be configured to mass concentration and be 0.5～2% solution, get standby B component, to slowly add in the standby A component with the isopyknic B component of standby A component under stirring, the B component adds the back fully and continues to stir 2 hours, after stopping to stir, under 0.1 normal atmosphere, 50 ℃ of dryings 2 hours, solvent evaporates gets the exsiccant modified manometer silicon dioxide.
2, preparation method according to claim 1 is characterized in that standby B component is following B
1, B
2, B
3, B
4In any one:
1. with number-average molecular weight be 100,000 HDPE to be dissolved in boiling range be in 60～90 ℃ the sherwood oil, be configured to mass concentration and be 0.5～2% HDPE petroleum ether solution, standby B
1Component;
2. with number-average molecular weight be 100,000 isotactic PP to be dissolved in boiling range be in 60～90 ℃ the sherwood oil, be configured to mass concentration and be 0.5～2% isotactic PP petroleum ether solution, standby B
2Component;
3. be that 10,000 nylon 1010 is dissolved in the acetone with number-average molecular weight, be configured to mass concentration and be 0.5～2% nylon 1010 acetone soln, standby B
3Component;
4. be that 10,000 poly(propylene oxide) is dissolved in the ethyl acetate with number-average molecular weight, be configured to mass concentration and be 0.5～2% poly(propylene oxide) ethyl acetate solution, standby B
4Component.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066861A (en) * | 1991-05-18 | 1992-12-09 | 格雷斯有限公司 | Soft silica of improvement and preparation method thereof and anticlogging agent |
| EP0926210A1 (en) * | 1997-12-19 | 1999-06-30 | Wacker-Chemie GmbH | Silicon oxide bearing on its surface partially or completely sylilated polysilicic acids chains |
| WO1999051692A1 (en) * | 1998-04-03 | 1999-10-14 | Grace Gmbh | Matting agents based on coated silicon dioxide |
| EP1284277A1 (en) * | 2001-08-08 | 2003-02-19 | Degussa Aktiengesellschaft | Silica-coated metal oxide particles |
| CN1407026A (en) * | 2001-08-19 | 2003-04-02 | 章浩龙 | Preparation method of superfine silicon dioxide powder |
| CN1408640A (en) * | 2001-09-20 | 2003-04-09 | 德古萨公司 | High BET/CTAB rate precipitation of silicon dioxide |
| CN1488682A (en) * | 2002-09-06 | 2004-04-14 | 德古萨公司 | Efficient delusterant based on precipited silicon dioxide |
-
2005
- 2005-01-18 CN CNB2005100181703A patent/CN1330714C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066861A (en) * | 1991-05-18 | 1992-12-09 | 格雷斯有限公司 | Soft silica of improvement and preparation method thereof and anticlogging agent |
| EP0926210A1 (en) * | 1997-12-19 | 1999-06-30 | Wacker-Chemie GmbH | Silicon oxide bearing on its surface partially or completely sylilated polysilicic acids chains |
| WO1999051692A1 (en) * | 1998-04-03 | 1999-10-14 | Grace Gmbh | Matting agents based on coated silicon dioxide |
| EP1284277A1 (en) * | 2001-08-08 | 2003-02-19 | Degussa Aktiengesellschaft | Silica-coated metal oxide particles |
| CN1407026A (en) * | 2001-08-19 | 2003-04-02 | 章浩龙 | Preparation method of superfine silicon dioxide powder |
| CN1408640A (en) * | 2001-09-20 | 2003-04-09 | 德古萨公司 | High BET/CTAB rate precipitation of silicon dioxide |
| CN1488682A (en) * | 2002-09-06 | 2004-04-14 | 德古萨公司 | Efficient delusterant based on precipited silicon dioxide |
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