CN100379815C - PVC foaming stabiliser and its preparation method - Google Patents
PVC foaming stabiliser and its preparation method Download PDFInfo
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- CN100379815C CN100379815C CNB2005101154084A CN200510115408A CN100379815C CN 100379815 C CN100379815 C CN 100379815C CN B2005101154084 A CNB2005101154084 A CN B2005101154084A CN 200510115408 A CN200510115408 A CN 200510115408A CN 100379815 C CN100379815 C CN 100379815C
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Abstract
The present invention provides a Ca/K/Zn type composite stabilizing agent and a preparation method thereof. The stabilizing agent based on 100 portions by weight comprises 0.2 to 0.8 portion of calcium, 0.2 to 2 portions of zinc, 0.2 to 1.8 portions of potassium, 5 to 25 portions of lubricant, 5 to 25 portions of modified resin and 0 to 50 portions of dispersing agents. The stabilizing agent of the present invention has the advantage of favorable stability. The stabilizing agent of the present invention can increase foaming speed and reduce foaming time, foam holes in obtained products are uniform and compact without indicated corrugation and punching holes, and prepared products have the advantages of smooth surface, stable color, little color deviation, good hand feel and elasticity, and production cost can be greatly reduced.
Description
Technical field
The invention provides a kind of PVC foaming stabiliser, and preparation method thereof.Particularly, the invention provides a kind of new calcium with good stability, potassium, zinc composite stabilizer, and preparation method thereof.
Background technology
The PVC product has good mechanics mechanical property because of it, good weather-proof (uvioresistant) performance, lightweight, long service life, low incendivity, low maintainability, low price and being widely used.Polyvinyl chloride (PVC) since its molecular structure to thermally labile, need to add stablizer to prevent or to slow down PVC thermal destruction in the course of processing, and can also prevent the destruction that the PVC goods in use cause because of light, heat, oxygen, keep its physicals.PVC stablizer commonly used comprises heavy metal stabilizer, but these metal(lic)stabilizers are very serious to the pollution of environment, and in recent years, use has been under an embargo in many countries and regions.
Therefore, the nothing of PVC thermo-stabilizer poisons striving direction and mainly concentrates on organotin and calcium/zinc composite heat stabilizer two aspects, and all makes significant progress.A remarkable advantage of calcium-zinc composite stabilizing agent section bar is that it has better weather.
Summary of the invention
One of purpose of the present invention provides a kind of stablizer that is used for the PVC foaming with superregulated property.
Another object of the present invention provides a kind of method for preparing the aforementioned stable agent.
According to a technical scheme of the present invention, based on the stablizer of 100 weight parts, stablizer of the present invention comprises: the lubricant of the zinc of the calcium of 0.2～0.8 weight part, 0.2～2 weight part, the potassium of 0.2～1.8 weight part and 5～25 weight parts, the modified resin of 5～25 weight parts, the dispersion agent of 0～50 weight part.
Preferably, stablizer according to the present invention comprises the calcium of 0.4～0.7 weight part, the zinc of 1.0～1.5 weight parts, the potassium of 1.0～1.5 weight parts and the lubricant of 10～15 weight parts, the modified resin of 10～15 weight parts, the dispersion agent of 20-40 weight part.
More preferably, stablizer according to the present invention comprises the calcium of 0.4 weight part, the potassium of 1.3 weight parts, the zinc of 1.5 weight parts, the polyisobutyl methacrylate of 15 weight parts, the calcium stearate of 15 weight parts, the stearic acid of 5～15 weight parts, the lime carbonate of 50 weight parts.
According to stablizer of the present invention, wherein, described modified resin can be for the conventional modified resin that uses in this area, as acrylic acid modified resin, methacrylic acid modified resin, phenylethene modified resin, modified rosin resin, organosilicon polyester modified resin, phenolic modified resin, modified epoxy etc.
According to stablizer of the present invention, wherein, described lubricant can be for the conventional lubricant that uses in this area, as stearate, paraffin etc.
According to stablizer of the present invention, wherein said dispersion agent can be the conventional dispersion agent that uses in this area, as lime carbonate etc.
According to another technical scheme of the present invention, the present invention also provides the method for preparing the aforementioned stable agent, this method may further comprise the steps: a) based on the mixture of 100 weight parts, mix the calcium of 2～8 weight parts, the zinc of 2～20 weight parts, the potassium of 2～18 weight parts in solvent; B) based on the said mixture of 100 weight parts, with the modified resin of gained mixture and 50～250 weight parts, the lubricant of 50～250 weight parts and the dispersant of 0～500 weight part, wherein said solvent is phosphorous acid ester, epoxy soybean oil, oxidation inhibitor.
According to technical scheme of the present invention, stablizer of the present invention can be used for the foaming of various PVC products.As required, stablizer of the present invention can be made the stablizer that is used to foam of high foamability, middle expansion ratio and low expansion ratio by the ordinary skill in the art.At the high foamed products of preparation, can use according to whipping agent of the present invention during as flooring laminate, automobile-used leather, thick product foaming leather, its expansion ratio is 3～5 times, and every day, every can save 2～3 tons of raw materials, adds up to and saves 0.8～10,000 yuan.When fast foaming, can use according to whipping agent of the present invention, can accelerate 5～10 meters of the expansion rates of baking oven, add up to the every day, every can fecund 2000～3000 meters, make profits 0.1～0.2 ten thousand yuan more.Can also be used for according to stablizer of the present invention in the preparation of low expansion ratio, as, sofa artificial leather, luggage leather, footwear leather, expansion ratio is 1～3, every day, every can save 0.3～0.5 ten thousand yuan.Further, can use according to stablizer of the present invention in outlet and high-grade environmentfriendly products, every meter profit can increase by 0.1～0.5 yuan, and adding up to increase every day, every profit 0.3～0.5 ten thousand yuan.And foaming stabiliser preparation method of the present invention is simple, raw materials cost reduces, so the cost of the present conventional foaming stabiliser that uses of its cost per ton ratio reduces by 3000～5000 yuan.
In the foaming of the PVC of routine goods,, thereby in calendered film production, cause shortcomings such as plasticizing is insufficient, uneven distribution even, easy-to-draw production well because Butut, the soft or hard of raw materials used model differ, melt flow rate (MFR) is different with recovered frequency.And contained Ba in the reworked material, organotin, high rare earth-stabilized dosage are very big to the influence of foaming, make bubble-hole thickness, expansion ratio is low, processing temperature is high, waste material etc.Further, when reworked material as three salt, disalt, with Pb, when Zn content is high, easily form the macropore bubble, cause perforation, poor, the surperficial material after-treatment consumption of surface quality is big, than great, yield poorly, problem such as cost height, and can overcome the problems referred to above owing to having splendid stabilising effect according to foaming stabiliser of the present invention.
Because of regeneration PVC reclaimed materials majority is based on fourth fat (DBP) class softening agent, flash-point low (170 degree--180 degree).Enter baking oven at 210 degree when rolling into foamed thin sheet---230 degree 45 " during above foaming, part DBP volatilization, the result make the product feel poor, stiff, shrinkage phenomenon (thickness low LCL) etc. is arranged after cooling off.Add the volatile quantity that foaming stabiliser of the present invention can make film foaming fast, reduce DBP, obtain high resilience, product that feel is soft.Accelerate the baking oven expansion rate, reduce foamed time, more effective raising output.
Foaming stabiliser of the present invention has good intermiscibility with regeneration PVC, promotes evenly plasticizing synchronously, shortens the fusion time, improves its stability, reduces the deposition of mechanical surface or separate out, and can improve filling adding amount.
The wide easy handling of foaming stabiliser setting range of the present invention, under the rolling processing temperature, material have outstanding hot strength and bounding force, fully plasticizing, film thin and thick evenly, not roll banding, improve tensile strength, but faster production.
Use foaming stabiliser of the present invention, need not to add other auxiliary agent, can obtain evenly fine and closely woven abscess, overcome external waviness, product surface is smooth, significantly reduce high magnification product surface perforation phenomenon, stablize color and luster, the color and luster deviation that reduces to cause in the foaming process, make the surface-treated material economy, improve the quality of production.
Foaming stabiliser of the present invention can increase 10--20%Ca in the multiple rete of reworked material, effect is all good, improves weathering resistance, keeps the original performance of PVC goods.
Can be according to PVC product, quality, expansion ratio Butut and the corresponding foaming stabiliser of the present invention of choose reasonable.Adjust the consumption of stablizer of the present invention according to the quality of reworked material.In the polyvinyl chloride resin foam leather, adjust the consumption of stablizer according to Ca consumption size, that recommends stablizer is used to 3～10wt%, preferred 3.5～5wt%.
According to the needs of actual PVC goods, foaming stabiliser of the present invention can contain Ba, for example, and for low-grade PVC goods.
Can be used for the calendering foaming, be coated with and scrape foaming and common foaming according to foaming stabiliser of the present invention.
Embodiment
Embodiment 1
The calcium of 2 weight parts, the zinc of 2 weight parts, the potassium of 2 weight parts are dissolved in the phosphorous acid ester of 20 weight parts, add the antioxidant of 5 weight parts, obtain mixture.Based on the said mixture of 100 weight parts, add the polyisobutyl methacrylate of 50 weight parts, the Zinic stearas of 50 weight parts and the lime carbonate of 50 weight parts, make stablizer then according to conventional methods.
Embodiment 2
The potassium of the zinc of the calcium of 8 weight parts, 20 weight parts, 18 weight parts is dissolved in the epoxy soybean oil of the phosphorous acid ester of 40 weight parts and 40 weight parts, adds the antioxidant of 10 weight parts, obtain mixture.Based on the said mixture of 100 weight parts, add the lime carbonate of Zinic stearas, 50 weight part stearic acid and 500 weight parts of polyisobutyl methacrylate, 250 weight parts of 250 weight parts, make stablizer then according to conventional methods.
Embodiment 3
The potassium of the zinc of the calcium of 4 weight parts, 10 weight parts, 10 weight parts is dissolved in the epoxy soybean oil of the phosphorous acid ester of 30 weight parts and 50 weight parts, adds the antioxidant of 8 weight parts, obtain mixture.Based on the said mixture of 100 weight parts, add the lime carbonate of Zinic stearas, 150 weight part stearic acid and 200 weight parts of polyisobutyl methacrylate, 100 weight parts of 100 weight parts, make stablizer then according to conventional methods.
Embodiment 4
The potassium of the zinc of the calcium of 7 weight parts, 15 weight parts, 15 weight parts is dissolved in the epoxy soybean oil of the phosphorous acid ester of 30 weight parts and 50 weight parts, adds the antioxidant of 8 weight parts, obtain mixture.Based on the said mixture of 100 weight parts, add the lime carbonate of Zinic stearas, 100 weight part stearic acid and 400 weight parts of polyisobutyl methacrylate, 150 weight parts of 150 weight parts, make stablizer then according to conventional methods.
The test implementation example
The foaming stabiliser that is obtained by above embodiment 1～4 is white dustless powder, low toxicity or nontoxic, density 1.8-2g/mm
3Neutral, fusing point 110--135 ℃, decomposition temperature is 230～280 ℃.
Compare with the PVC goods that use conventional foaming stabiliser preparation, use of the present invention stable Agent increases expansion rate, reduces foamed time, and the abscess in the product of acquisition is fine and closely woven, nothing evenly Show ripple, do not have the perforation phenomenon, product surface is smooth, color and luster is stable, the color and luster deviation is minimum, Product good hand touch, high resilience.
Claims (3)
1. one kind is used for the stablizer that PVC foams, it is characterized in that, stablizer based on 100 weight parts comprises: the lubricant of the zinc of the calcium of 0.2～0.8 weight part, 0.2～2 weight part, the potassium of 0.2～1.8 weight part and 5～25 weight parts, the modified resin of 5～25 weight parts, the dispersion agent of 0～50 weight part.
2. according to the PVC foaming stabiliser of claim 1, it is characterized in that, stablizer based on 100 weight parts comprises: the lubricant of the zinc of the calcium of 0.4～0.7 weight part, 1.0～1.5 weight parts, the potassium of 1.0～1.5 weight parts and 10～15 weight parts, the modified resin of 10～15 weight parts, the dispersion agent of 20-40 weight part.
3. according to the PVC foaming stabiliser of claim 1, it is characterized in that, stablizer based on 100 weight parts comprises: the polyisobutyl methacrylate of the potassium of the calcium of 0.4 weight part, 1.3 weight parts, the zinc of 1.5 weight parts, 15 weight parts, the calcium stearate of 15 weight parts, the stearic acid of 5～15 weight parts, the lime carbonate of 50 weight parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101154084A CN100379815C (en) | 2005-11-03 | 2005-11-03 | PVC foaming stabiliser and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101154084A CN100379815C (en) | 2005-11-03 | 2005-11-03 | PVC foaming stabiliser and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1763130A CN1763130A (en) | 2006-04-26 |
| CN100379815C true CN100379815C (en) | 2008-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005101154084A Expired - Fee Related CN100379815C (en) | 2005-11-03 | 2005-11-03 | PVC foaming stabiliser and its preparation method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102224192B (en) * | 2008-11-28 | 2013-06-12 | 三菱丽阳株式会社 | Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body |
| CN104004295B (en) * | 2014-05-12 | 2015-09-02 | 广州市联诺化工科技有限公司 | PVC wallpaper is with inspiring alveolitoid Liquid K/Zn composite thermal stabilizer and preparation method thereof |
| CN104497450A (en) * | 2014-12-30 | 2015-04-08 | 东莞市悠悠美居家居制造有限公司 | Anti-tear, anti-skid and environment-friendly password cloth and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04136054A (en) * | 1990-09-27 | 1992-05-11 | Asahi Denka Kogyo Kk | Stabilized chlorinated resin composition |
| CN1631963A (en) * | 2004-11-15 | 2005-06-29 | 四川大学 | Ca-Zn-Sn composite stabilizer for polyvinyl chloride and method for preparing same |
-
2005
- 2005-11-03 CN CNB2005101154084A patent/CN100379815C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04136054A (en) * | 1990-09-27 | 1992-05-11 | Asahi Denka Kogyo Kk | Stabilized chlorinated resin composition |
| CN1631963A (en) * | 2004-11-15 | 2005-06-29 | 四川大学 | Ca-Zn-Sn composite stabilizer for polyvinyl chloride and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 新型液体钙锌复合稳定剂的研究. 许林忠.塑料助剂，第6卷. 1997 * |
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