CN88101602A - With the Al-system coupling agent is the new type active calcium carbonate of properties-correcting agent - Google Patents
With the Al-system coupling agent is the new type active calcium carbonate of properties-correcting agent Download PDFInfo
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- CN88101602A CN88101602A CN198888101602A CN88101602A CN88101602A CN 88101602 A CN88101602 A CN 88101602A CN 198888101602 A CN198888101602 A CN 198888101602A CN 88101602 A CN88101602 A CN 88101602A CN 88101602 A CN88101602 A CN 88101602A
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Abstract
The present invention system is used for the preparation method of a class new type active calcium carbonate of plastics, rubber, coating and printing ink etc.With the novel aluminum system coupling agent is properties-correcting agent, with the organism that contains tool arc electron pair atoms such as oxygen, nitrogen, sulphur, phosphorus is synergist and the new type active calcium carbonate that adds necessary processing aid, it is big to have amount of filling, dispersed good with processibility, the water-intake rate low oil absorption ferric is little, look shallow, thermostability is high, the simple and low characteristics of cost of technology.Be applied to above-mentioned composite product, can play the saving resin, improve performance, the energy-conservation and effect that reduces cost.
Description
The present invention relates to the Al-system coupling agent is the preparation method of the new type active calcium carbonate of properties-correcting agent.
Lime carbonate is most important mineral filler and the properties-correcting agent in plastics, rubber, coating, printing ink and the various composite industry.Lime carbonate was many as weighting agent, only play increment and reducing cost in the past.In recent years, along with developing rapidly and global energy shortage of matrix material, with the oil is lasting rise in price of synthetic resins of raw material, require people in composite products such as plastics, rubber, to dose more mineral filler, with further reduction goods cost, save resin demand, and require when dosing more mineral filler, to guarantee or improve the processing characteristics and the physical and mechanical properties of goods.The water-ground limestone that light calcium carbonate that the present common precipitator method are produced or mechanical milling method are produced can't reach above-mentioned requirements.Therefore how to change the production technique of lime carbonate and product is carried out modification to obtain high performance lime carbonate, promptly so-called treated carbonates, the important topic that has become domestic and international filler research and produced.The research of this respect, Japan maintains the leading position in the world.The method for making of " superfine activated calcium carbonate " has just been invented by Japan as far back as nineteen twenty-seven, develops the product that carries out surface modification with stearic acid, and develops the product of different crystal forms, different grain size and different surfaces modification later on again successively in 1933.In recent years after U.S.'s this respect research is also very active, especially the seventies titanate coupling agent is invented, played very big promoter action to treated carbonates and in plastics, the industrial applied research of rubber coating.
China produces 30 to 500,000 tons in lime carbonate at present, the overwhelming majority is unmodified light calcium carbonate, the development of minority unit is just just arranged in recent years and produced several fine carbon or the modification kind of using for rubber, and having only with stearic acid-treated treated carbonates that the confession plastic industry is used is a kind of, up to 85 years, just have Nanjing make a leapleap forward refining grey factory etc. produce with titanate coupling agent handle such as NY series treated carbonates.So far, China's pearl filler still can not satisfy the production demand far away aspect quality and variety.
The modification of lime carbonate, the domestic and international method that adopts is concluded two classes: the one, change the lime carbonate production technique, little and dispersed little fine or calcium carbonate superfine powder with the production granularity; Another kind of is to add a postprocessing working procedures after original production process, with various properties-correcting agent lime carbonate is carried out the surface active modification and handles.First kind method must be transformed old technology, and facility investment is big, the product cost height; Second class methods, equipment is simple, less investment, and it is low to consume energy, and cost is low, equally also can obtain the treated carbonates of better performances.In one class methods of back, topmost key is the selection of properties-correcting agent, so far be used as the following a few class material that has of calcium carbonate surface modifying agent: lipid acid, resinous acid and metallic salt thereof, ester class or its mixture, high fatty alcohol, alkylsulphonic acid, alkylphosphonic acid carboxylic acid, organic amino, polyoxyethylene glycol and one ester and tensio-active agent etc.; The multipolymer of polyacrylic acid, toxilic acid and iso-butylene, vinylbenzene or vinyl acetate and metal-salt thereof or part ester, half amide based compound etc., these properties-correcting agent, mainly be to form a physics coat on the lime carbonate surface, a kind of lubrication that between lime carbonate and organic resin interface, produces, improving the processing characteristics of goods, but improve little to the physical and mechanical properties of goods after the moulding.Coupling agents such as the titanic acid ester that occurs behind the seventies, phosphoric acid ester, boric acid ester, stannic acid ester, zirconium aluminate.Because can on lime carbonate surface and organic resin body chemical reaction or physics chemical action take place, improve the processing characteristics and the physical and mechanical properties of composite product.And obtained increasingly extensive application, wherein with titanate coupling agent research with use morely.But the titanate coupling agent intrinsic colour is darker, and modified calcium carbonate easily makes its whiteness reduce; Can be when some polymkeric substance uses because of the oxidation variable color; Because of hydrolytic activity is bigger, during storage or in the mixing course of processing of material, hydrolysis or alcoholysis take place easily; And production cost and price are more high; In addition, because of titanic acid ester is thick liquid more, metering and use inconvenience when lime carbonate is carried out modification, must be used thinner and adopt spray art reinforced, make complex process, and have polluted environment because of thinner volatilizees.Though, DGHawthorne(u, s, p, 3,905,936) also adopted the organoaluminum derivative as surface-treated agent, the organoaluminum derivative that they adopted, water-disintegrable too big, can only use up at short notice; Be difficult in practice be used.
At the problems referred to above, the objective of the invention is to provides a kind of applied range by being properties-correcting agent with the Al-system coupling agent, and production technique is simple, the treated carbonates that is applicable to plastics, rubber, coating and printing ink etc. of the low and excellent combination property of cost.
Treated carbonates preparation method provided by the invention solves by following scheme:
1, adopts the Al-system coupling agent (Chinese patent application number: 85102942) of this invention people invention
Structural formula is:
When Al-system coupling agent carries out surface treatment to lime carbonate, because of it can react with lime carbonate surface proton (hydroxyl that is produced by unimolecular layer water or lime carbonate surface hydrolysis provides), make the lime carbonate surface by alkalescence hydrophilic strong polarity become organophilic in or low polarity.React as follows:
Therefore treated carbonates and the organic resin after the modification has good affinity, and the usage quantity of Al-system coupling agent is the 0.30-2.5% of weight of calcium carbonate usually.
2, in order to strengthen the modified effect of Al-system coupling agent to the lime carbonate surface, adopted to contain organism that aerobic, nitrogen, sulphur, phosphorus etc. have the lone electron pair atom as synergist, they are Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol, resinous acid, lipid acid, aromatic acid and its esters, ester class or its mixture; Organic amine or its salt, ketone and tensio-active agent etc.This class material can be good for and a synergy by contained lone electron pair and coupling agent central metal atom aluminium formation coordination.The usage quantity of synergist is the 0.30-2.5% of lime carbonate.
3, in order further to improve the processing characteristics of the matrix material of dosing treated carbonates, the processing aid below in new type active calcium carbonate, having adopted: white oil, paraffin, turbine oil, machine oil, DOP, DBP and polyvinyltoluene, polystyrene, polyvinyl acetate (PVA), oxidic polyethylene, ACR, MBS, chlorinatedpolyethylene, chlorinated rubber, poly-(methyl) esters of acrylic acid, terpine resin and terpenes-styrol copolymer.The usage quantity of processing aid is the 0.50-8.5% of lime carbonate.
4, use the dry modification process that simply and efficiently directly adds properties-correcting agent, synergist and processing aid without thinner.This method is in the high-speed mixing equipment of tool high shear force lime carbonate to be carried out modification under 80 ℃-150 ℃.
In sum, provided by the invention is that the treated carbonates of properties-correcting agent has following prescription (is 100% with weight of calcium carbonate) in the Al-system coupling agent.
Lime carbonate 100
Al-system coupling agent 0.30-2.5%
Synergist 0.30-2.5%
Processing aid 0.50-8.5%
The present invention compares with technology in the past, because (Chinese patent application number is: 85102942 to have adopted Al-system coupling agent, and the patent of invention of having applied for the U.S., Japan, West Germany, France and Britain) is the surface-modifying agent of lime carbonate, and be equipped with synergist, processing aid, directly to add the dry modification process of properties-correcting agent, synergist and processing aid without thinner, have simple, efficient, the safe and free of contamination characteristics of technology.Treated carbonates whiteness height after the modification, water-intake rate is low, and amount of filling is big, processibility good, and thermostability height and cost are lower.
The present invention can be further specified by following two embodiment.
Embodiment 1
In GRH-500 type high-speed mixer, the lime carbonate that adds 100 kilograms, under 110 ℃-130 ℃, uncovered high-speed stirring 10 minutes, divide three times then 0.75 kilogram Al-system coupling agent (as aluminate coupling agent DL-411-A) added high-speed mixer, add 0.75 kilogram of stearic acid after three minutes, one kilogram of fusing point of adding is 95-100 ℃ a oxidic polyethylene after two minutes, discharging after three minutes, the new type active calcium carbonate that obtains with paraffin wax in (1: 2) viscosity be 270 centipoises, unmodified lime carbonate then surpasses 100,000 centipoises in the same system medium viscosity.
Embodiment 2
In GRH-500 type high-speed mixer, the lime carbonate that adds 100 kilograms, under 110 ℃-130 ℃, uncovered high-speed stirring 10 minutes, divide three times then with in 1.3 kilograms Al-system coupling agent (as aluminate coupling agent DL-411-D) the adding high-speed mixer, after three minutes, add 0.75 kilogram of palmitinic acid, add one kilogram of polyvinyltoluene resin after three minutes.Discharging after three minutes, the new type active calcium carbonate that obtains (1: 2) viscosity in DOP is 740 centipoises, and unmodified lime carbonate surpasses 100,000 centipoises in the same system medium viscosity.
Claims (6)
1, the present invention relates to contain the new type active calcium carbonate preparation method of lime carbonate, properties-correcting agent, synergist and processing aid etc., it is characterized in that with the novel aluminum system coupling agent be filling modifier, increased synergist and processing aid, and adopt dry modification process.
2, the properties-correcting agent among the treated carbonates preparation method according to claim 1 is characterized in that properties-correcting agent is to use the novel aluminum system coupling agent, and its usage quantity is the 0.30-2.5% of lime carbonate.
3, the synergist among the treated carbonates preparation method according to claim 1 is characterized in that adopting the Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol, resinous acid, lipid acid, aromatic acid and its esters that contain tool lone electron pair atoms such as oxygen, nitrogen, sulphur, phosphorus, ester class and composition thereof; Organic amine or salt, ketone and tensio-active agent etc., the consumption of synergist is the 0.30-2.5% of lime carbonate consumption.
4, the processing aid among the treated carbonates preparation method according to claim 1 is characterized in that having adopted white oil, paraffin wax, turbine oil, machine oil, DOP, DBP and polyvinyltoluene, polystyrene, polyvinyl acetate (PVA), oxidic polyethylene, ACR, MBS, chlorinatedpolyethylene, chlorinated rubber, poly-(methyl) esters of acrylic acid, terpine resin and terpenes-styrol copolymer.Its consumption is the 0.50-8.5% of weight of calcium carbonate.
5, according to the modified technique among the treated carbonates preparation method described in the claim 1, it is characterized in that, and directly add the dry modification process of properties-correcting agent, synergist and processing aid without thinner.Modification is under 80 ℃-150 ℃, has in the high-speed mixing machine equipment of high shear force to carry out.
6,, it is characterized in that having following prescription (is 100% in weight of calcium carbonate) according to the treated carbonates preparation method described in the claim 1,2,3 and 4
Lime carbonate 100
Al-system coupling agent 0.30-2.5
Synergist 0.30-2.5
Processing aid 0.50-8.5
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198888101602A CN88101602A (en) | 1988-03-22 | 1988-03-22 | With the Al-system coupling agent is the new type active calcium carbonate of properties-correcting agent |
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| CN198888101602A CN88101602A (en) | 1988-03-22 | 1988-03-22 | With the Al-system coupling agent is the new type active calcium carbonate of properties-correcting agent |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN101838479A (en) * | 2010-03-19 | 2010-09-22 | 福建师范大学 | Method for preparing dispersible ultra-fine silicon dioxide |
| CN105199431A (en) * | 2015-09-22 | 2015-12-30 | 亚士漆(上海)有限公司 | Calcium carbonate activating method and environment-friendly single-component putty |
| CN107936400A (en) * | 2017-12-22 | 2018-04-20 | 贺州市星辉科技有限公司 | A kind of function pearl filler and preparation method thereof |
| CN108084738A (en) * | 2017-12-22 | 2018-05-29 | 贺州市星辉科技有限公司 | It is a kind of to be modified the calcium carbonate prepared and its method using composite coupler |
| CN108084501A (en) * | 2017-12-22 | 2018-05-29 | 贺州市星辉科技有限公司 | A kind of pearl filler and preparation method thereof |
| CN108102140A (en) * | 2017-12-22 | 2018-06-01 | 贺州市星辉科技有限公司 | A kind of activated Calcium carbonate and preparation method thereof |
| CN108102141A (en) * | 2017-12-22 | 2018-06-01 | 贺州市星辉科技有限公司 | It is a kind of suitable for modified calcium carbonate filler of plastics and preparation method thereof |
| CN108129882A (en) * | 2017-12-22 | 2018-06-08 | 贺州市星辉科技有限公司 | A kind of method for preparing function calcium carbonate using modified coupling agent |
| CN108129883A (en) * | 2017-12-22 | 2018-06-08 | 贺州市星辉科技有限公司 | A kind of surface-active-modified function calcium carbonate and preparation method thereof |
-
1988
- 1988-03-22 CN CN198888101602A patent/CN88101602A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838479A (en) * | 2010-03-19 | 2010-09-22 | 福建师范大学 | Method for preparing dispersible ultra-fine silicon dioxide |
| CN101838479B (en) * | 2010-03-19 | 2013-11-20 | 福建师范大学 | Method for preparing dispersible ultra-fine silicon dioxide |
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN101830494B (en) * | 2010-05-11 | 2013-08-21 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN105199431A (en) * | 2015-09-22 | 2015-12-30 | 亚士漆(上海)有限公司 | Calcium carbonate activating method and environment-friendly single-component putty |
| CN107936400A (en) * | 2017-12-22 | 2018-04-20 | 贺州市星辉科技有限公司 | A kind of function pearl filler and preparation method thereof |
| CN108084738A (en) * | 2017-12-22 | 2018-05-29 | 贺州市星辉科技有限公司 | It is a kind of to be modified the calcium carbonate prepared and its method using composite coupler |
| CN108084501A (en) * | 2017-12-22 | 2018-05-29 | 贺州市星辉科技有限公司 | A kind of pearl filler and preparation method thereof |
| CN108102140A (en) * | 2017-12-22 | 2018-06-01 | 贺州市星辉科技有限公司 | A kind of activated Calcium carbonate and preparation method thereof |
| CN108102141A (en) * | 2017-12-22 | 2018-06-01 | 贺州市星辉科技有限公司 | It is a kind of suitable for modified calcium carbonate filler of plastics and preparation method thereof |
| CN108129882A (en) * | 2017-12-22 | 2018-06-08 | 贺州市星辉科技有限公司 | A kind of method for preparing function calcium carbonate using modified coupling agent |
| CN108129883A (en) * | 2017-12-22 | 2018-06-08 | 贺州市星辉科技有限公司 | A kind of surface-active-modified function calcium carbonate and preparation method thereof |
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