CN1061030A - Modified rubber plastics raw material and preparation method thereof - Google Patents
Modified rubber plastics raw material and preparation method thereof Download PDFInfo
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- CN1061030A CN1061030A CN 90108295 CN90108295A CN1061030A CN 1061030 A CN1061030 A CN 1061030A CN 90108295 CN90108295 CN 90108295 CN 90108295 A CN90108295 A CN 90108295A CN 1061030 A CN1061030 A CN 1061030A
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Abstract
The invention discloses a kind of modified rubber plastics raw material and manufacture method thereof, this method and comprise with hydro carbons lubricating substance and/or organic carboxyl acid mass treatment calcium carbonate powders or silicate powder, when handling above-mentioned powder or after handling, add coupling agent or add softening agent again, in homogenizer, be kneaded into powder-material; And then mix with an amount of Plastic Resin and rubber nylon, use two (list) screw extrusion presss to extrude pelletizing or, become bulk goods at last with pelletizing behind the plasticator compressing tablet.
Description
The present invention relates to a kind of modified rubber plastics raw material and preparation method thereof, particularly relate to and a kind of rubber plastic is had good affinity and dispersiveness, and can improve fill composition of rubber plastic performance and preparation method thereof.
As everyone knows, lime carbonate and silicate are a kind of mineral fillers commonly used, with other mineral facies ratio, lime carbonate and silicate have advantages such as the source is wide, cost is low, nontoxic, look shallow, reasonably use lime carbonate and silicate filler can improve the plastic, rubber performance to greatest extent, save the synthetic resin rubber raw material, save energy also can reduce cost.
In recent years, people attempt to adopt economic method always, improve lime carbonate and the loading level of silicate filler in plastic, rubber as much as possible by using powerful stirrer.Yet the loading level of this two classes filler in rubber plastic is not very high so far, and the dispersion of filler in plastics is also inhomogeneous.
Someone advise with insatiable hunger close and or saturated middle high molecular weight carboxylic (as butanic acid, lauric acid etc.) handle and grind meticulous natural whiting, make it change into sulfonate, vitriol or other material (French Patent 1047087).Yet people have confirmed the lime carbonate that this method was handled, can not increase the content of mineral filler in plastics or rubber significantly.
Afterwards, the someone advised using the linking agent treatment inorganic filling material when the preparation pearl filler, made and produced good intermiscibility between hydrophilic mineral filler and the hydrophobic polymer.(German patent DE 2735160) that this linking agent is made up of the organic phosphine of phosphonic acid ester or phosphonic acids type.However, fact proved, even adopt such linking agent can not reach the improvement effect of expection.Promptly the intermiscibility between hydrophilic inorganic filler and hydrophobic polymer is not improved significantly.Therefore, some mechanical characteristics of these compositions imperfection still.
In order to overcome above-mentioned shortcoming, people had once used the whole bag of tricks, as select the powder or the particle of uniform particle diameter, or filler carried out surface treatment etc., but the former usually produces secondary aggregation because of the affinity difference of powder and organic polymer, causes concocting inhomogeneous, disperse shortcomings such as relatively poor, thereby make the improvement in performance effect of organic polymer resin and rubber little.And the latter carries out surface treatment with damp process to powder, particle, but the shortcoming of this damp process is preparation method's complexity, and efficient is low, the cost height.
At above-mentioned shortcoming, the inventor has continued to do a large amount of careful research work.But the lime carbonate of filling with the new combination searching high-content in the known or still unknown method and silicate inorganic filler and preparation method thereof.Found a kind ofly, stirred with coupling agent and softening agent again with the absorption of calcium carbonate powders or silicate powder or in conjunction with hydro carbons lubricating substance or organic carboxyl acid and derivative thereof.And then stir with a spot of selected plastic, rubber and to mediate evenly, and with the novel method of singly (two, many) screw pelletizer granulation (behind the also available hot mastication machine compressing tablet, the method for cutting into pieces with dicing machine) again.Found the new way that obtains excellent dispersiveness and affinity, surface property and other raising impact of performance.
More particularly, stir with 100 parts of 90-825 purpose lime carbonate (or silicate) powder hydro carbons lubricant or organic carboxyl acid series lubricant agent with 1-4 part under normal temperature to 60 ℃ temperature, when stirring or after stirring, add 0.3-11 part coupling agent and the kneading of 3-2600 part softening agent, make powder particle surface form a coating layer, be powder-material.And then with an amount of (for example 5～1600 parts), rubber or plastic nylon restir powdering material or granulation in two (single, double) screw pelletizer together, whole process is approximately with 5 minutes.Or cut into slices again with the plasticator compressing tablet.
Method of the present invention is to make filling adsorption in advance or in conjunction with required lubricant, softening agent and coupling agent, and handles filler with an amount of selected plastic, rubber, thereby can improve the blending of filler to selected rubber plastic significantly.But be filled in the selected rubber plastic high-content, thereby make selected plastic, rubber performance that bigger improvement be arranged.Selected plastic, rubber type when the term here " selected " is meant in actual applications.
Calcium carbonate powders or silicate powder used in the present composition and the method are meant that fineness is 90-825 purpose lime carbonate or silicate powder.Lime carbonate and silicate powder used among the present invention are meant heavy or ground calcium carbonate, white pottery powder, talcum powder, wollastonite powder, glass yarn staple fibre, glass powder, white marble powder, granite powder, mica powder, glass microballon, cement, and add tinting material (as titanium dioxide, laterite, loess, ultramarine, carbon black, and other chemical stainings etc.) as required.
Hydro carbons lubricant used in the present composition and the method has whiteruss, native paraffin, microcrystalline wax, clorafin, hydrochloric ether etc., usually add with wherein a kind of paraffin or two or more mixtures, its consumption can suitably be adjusted according to application target and condition, but for giving full play to effect of the present invention, per 100 parts of lime carbonate or silicate powder can add 1-4 part, and are preferable range with 2-3 part.
Organic carboxyl acid material used in the present composition and the method thereof has calcium stearate, Zinic stearas, stearic acid, Palmiticacid, eicosanoic acid, linolic acid, and its optimum amount is that per 100 parts of lime carbonate or silicate powder are used 1-4 part, is good with 1-3 part especially.
Used softening agent has the dimethyl phthalate class in present composition and preparation method thereof, for example dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinoctyl phthalate, di (2-ethylhexyl) phthalate etc.; Fatty group dibasic acid, for example DID Su, Uniflex DBS, toxilic acid two (2-ethylhexyl), dibutyl fumarate; Can use wherein a kind of separately, also can severally mix use, the addition of softening agent is that 100 parts of lime carbonate or silicate powder are used 3-2600 part, with 3-4 part for well.
Used coupling agent is a titante coupling agent in present composition and preparation method thereof, for example: sec.-propyl three iso stearate base titanic acid ester, sec.-propyl three (lauryl-tetradecyl) titanic acid ester, sec.-propyl distearyl ylmethyl acryl titanic acid ester, sec.-propyl trimethylammonium acryl titanic acid ester, sec.-propyl triacryl titanic acid ester, silane coupling agent, enedioxy two (dioctyl is phosphate-based) titanium etc.; Its consumption is that per 100 parts of lime carbonate or silicate powder are used 0.3-11 part, the most handy 1-2 part.
Plastics (being selected plastics and rubber) used in the present composition and the method can be polyvinyl chloride, high-pressure polyethylene, low pressure polyethylene or polypropylene, polystyrene, polyolefine, polyamine fat etc., and rubber is natural rubber or synthetic chloroprene rubber.Its consumption is that per 100 parts of lime carbonate or silicate powder are used 5-1600 part, and the most handy 15-28 part is heavy.Rubber and resin number can compare number according to purposes adjustment.
The reagent that uses in the present composition and the method, be hydro carbons or organic carboxyl acid series lubricant agent, softening agent and coupling agent, for making it can adsorb equably or be combined on lime carbonate (or silicate) powder particle surface, in the hope of improving the affinity performance, use available No. 200 gasoline, water, ethanol, synthetic thinner, ether equal solvent dilution back, at this moment, the consumption of solvent is not more than three times of coupling agent consumption usually.Also can be without solvent.
About the preparation method of the present composition, can be in high-speed stirring mixer limit heated and stirred lime carbonate or silicate powder limit add above-mentioned all ingredients.Interpolation order as for reagent; lubricant, softening agent and coupling agent can add respectively; also can add simultaneously; but preferably be lubricated the processing of agent in advance; last again with an amount of selected Plastic Resin rubber fusion after reenter in single (two, many) screw pelletizer granulation or use two, multiple roll plasticator compressing tablet after, cut into pieces with slicing machine again.
With the feedstock composition of the inventive method preparation, almost can't see the secondary aggregation phenomenon, when with an amount of selected Plastic Resin rubber mix, show good glossiness, dispersed and with the affinity of used Plastic Resin rubber etc.In addition, its method for making of feedstock composition of the present invention (comprising powder and pellet) is simple, convenient, and owing to have fabulous dispersiveness, can realize the high density filling concerning selected Plastic Resin rubber, so, see it also is a kind of fabulous raw material from economic angle.
More than various raw materials mix in also can single adding plastic, rubber and use.
The following examples are to further specify of the present invention, rather than limitation of the present invention.
Embodiment 1
In 100 parts of adding homogenizers of 400 purpose light calcium carbonate powder; under 60 ℃ of temperature with 3 parts native paraffin lubricant; 3 parts dioctyl phthalate (DOP) softening agent and 2 parts sec.-propyl, three iso stearate base titanate coupling agents join in the above-mentioned homogenizer; stir and mediated 8 minutes; the stirrer rotating speed is 900rpm; the powder-material that stirring is obtained is a powder-material with 25 parts of polyvinyl chloride (PVC) RESINS and 40 parts of synthetic chloroprene rubber restir again; injecting twin screw extruder then plasticated 8 minutes; last extruder grain just can make the granular compound material of the rubber combined raw material of modified PVC resin.
Application examples 1
In twin-roll plastic mixing mill, plasticate with 150 parts of polyvinyl chloride (PVC) RESINS with 75 parts of the fillers that makes in the foregoing description and 90 parts respectively, time is 8 minutes, be that 120 ℃, die temperature are moulding on pressure forming machine under 120 ℃ of conditions at composition then, make polyvinyl chloride film, and test by GB1040-79 " plastic tensile test method ", it the results are shown in table 1.
As can be seen from Table 1, the filler with the inventive method preparation has good filling property and affinity and dispersed good for polyvinyl chloride (PVC) RESINS.
Embodiment 2
In 100 parts of adding homogenizers of glass powder with 800 order fineness; under 80 ℃ of temperature, 2 parts of clorafins, 4 parts of dibutyl phthalates, 1.5 parts of sec.-propyl trimethylammonium acryl titanic acid ester are joined in the above-mentioned homogenizer; stir and mediated 10 minutes; stirring velocity is 900rpm; stir into powder; and then stir with 28 parts of high-pressure polyethylenees; and then inject single (two, many) screw pelletizer and plasticated 8 minutes; extrude pelletizing then, just can make the high-pressure polyethylene fleut.
Embodiment 3
Make sole after mixing with 40 parts of the rubber of embodiment 1 and PVC60 part and 40 parts of wollastonites, its alternating bending tests sees Table 2.China National Light Industrial Products Department's ministerial standard is expansion 12mm.
Above embodiment just further specifies of the present invention, and any change that does not exceed spirit and scope of the invention all within the scope of the present invention.
Claims (9)
1, a kind of modified rubber plastics raw material composition, it is characterized in that said composition comprises 5～1600 parts of lime carbonate or 100 parts of silicate powders, 0.3～11 part of 1～4 part of coupling agent of hydro carbons lubricant organic carboxyl acid series lubricant agent, 3～2600 parts in softening agent, selected Plastic Resin or rubber, said umber all refers to parts by weight.
2, modified rubber plastics raw material composition according to claim 1, wherein the fineness of said calcium carbonate powders or silicate powder is 90～825 orders.
3, modified rubber plastics raw material composition according to claim 1, wherein said hydro carbons lubricating substance is whiteruss, native paraffin, microcrystalline wax, clorafin, hydrochloric ether, and its preferable amount is that per 100 parts of calcium carbonate powderss or silicate powder are with 0.3～8 part.
4, according to the said modified rubber plastics raw material composition of claim 1, wherein said organic carboxyl acid material is calcium stearate, Zinic stearas, stearic acid, Palmiticacid, eicosanoic acid, linolic acid, and its consumption is 0.4～3 part of per 100 parts of calcium carbonate powderss or a silicate powder.
5, modified rubber plastics raw material composition according to claim 1, wherein said softening agent has dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinoctyl phthalate, di (2-ethylhexyl) phthalate, DID Su, Uniflex DBS, toxilic acid (2～ethylhexyl), dibutyl fumarate, can be separately a kind of with wherein, also can severally mix use, its optimum amount is that per 100 parts of lime carbonate or silicate powder are with 3～2600 parts.
6; modified rubber plastics raw material composition according to claim 1, wherein said coupling agent has silane coupling agent; sec.-propyl three different fatty acyl group titanic acid ester; sec.-propyl three (lauryl-tetradecyl) titanic acid ester; titanate coupling agent OL-T671 type and OL-951 type; sec.-propyl distearyl ylmethyl acryl titanic acid ester; sec.-propyl trimethylammonium acryl titanic acid ester; sec.-propyl triacryl titanic acid ester; enedioxy two (dioctyl is phosphate-based) titanium; titanate coupling agent KR-TOES-201 and KR-TTS; its optimum amount is per 100 parts of calcium carbonate powderss or silicate powder with 0.3～11 part of weight.
7, modified rubber rubber material feedstock composition according to claim 1.It is per 100 parts of lime carbonate or silicate powder with 5～1600 parts of weights that wherein said Plastic Resin of selecting for use or rubber are respectively high and low polyethylene, polypropylene, polystyrene, polyolefine, polyamine fat, synthetic chloroprene rubber or natural rubber, polyvinyl chloride, its optimum amount of nylon.
8, according to the described modified rubber plastics raw material composition of the arbitrary claim of claim 1～7, wherein all silicate powders refer to white pottery powder, talcum powder, wollastonite powder, mica powder, perlite powder, glass powder, staple glass fibre, clay of all kinds, terra alba, cement, pulverized slag, white marble powder, granite powder, calcined clay, glass microballon.
9, a kind of modified rubber plastics raw material preparation of compositions method, it is characterized in that this method comprises with hydro carbons lubricating substance and/or organic carboxyl acid mass treatment calcium carbonate powders or silicate powder, when handling calcium carbonate powders or silicate powder or after handling, add coupling agent and softening agent, in homogenizer or mixing machine or heat seal pot or cylinder, mediate, be stirred into powder-material; Add an amount of Plastic Resin or rubber nylon again, mix the back with single, double or multiscrew tablets press granulation or with pair, behind multiple roll plasticator (the instant heating power tabletting machine) compressing tablet, break with slicing machine again and cut into pieces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108295 CN1061030A (en) | 1990-10-13 | 1990-10-13 | Modified rubber plastics raw material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108295 CN1061030A (en) | 1990-10-13 | 1990-10-13 | Modified rubber plastics raw material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1061030A true CN1061030A (en) | 1992-05-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90108295 Withdrawn CN1061030A (en) | 1990-10-13 | 1990-10-13 | Modified rubber plastics raw material and preparation method thereof |
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| CN (1) | CN1061030A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109066C (en) * | 1996-08-26 | 2003-05-21 | 株式会社普利司通 | Rubber composition and pneumatic tire made by using the same |
| CN101353448B (en) * | 2008-09-13 | 2010-09-29 | 山东东高纳米科技有限公司 | Dustfree demolding agent for high polymer elastic particle |
| CN104194404A (en) * | 2014-08-20 | 2014-12-10 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Active calcium silicate, and preparation method and application thereof |
| CN106084807A (en) * | 2016-06-01 | 2016-11-09 | 安徽强力重工起重机械有限公司 | A kind of rubber plastizing agent for Coal Transport machine wear resistant belt |
| CN106478992A (en) * | 2016-10-14 | 2017-03-08 | 无锡三帝特种高分子材料有限公司 | A kind of cosmetic package aluminizer |
| CN108298919A (en) * | 2018-04-10 | 2018-07-20 | 佛山市三水万瑞达环保科技有限公司 | A kind of modified polystyrene composite architectural materials and its production method |
-
1990
- 1990-10-13 CN CN 90108295 patent/CN1061030A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109066C (en) * | 1996-08-26 | 2003-05-21 | 株式会社普利司通 | Rubber composition and pneumatic tire made by using the same |
| CN101353448B (en) * | 2008-09-13 | 2010-09-29 | 山东东高纳米科技有限公司 | Dustfree demolding agent for high polymer elastic particle |
| CN104194404A (en) * | 2014-08-20 | 2014-12-10 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Active calcium silicate, and preparation method and application thereof |
| CN106084807A (en) * | 2016-06-01 | 2016-11-09 | 安徽强力重工起重机械有限公司 | A kind of rubber plastizing agent for Coal Transport machine wear resistant belt |
| CN106478992A (en) * | 2016-10-14 | 2017-03-08 | 无锡三帝特种高分子材料有限公司 | A kind of cosmetic package aluminizer |
| CN108298919A (en) * | 2018-04-10 | 2018-07-20 | 佛山市三水万瑞达环保科技有限公司 | A kind of modified polystyrene composite architectural materials and its production method |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WW01 | Invention patent application withdrawn after publication |