CN112029149B - Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof - Google Patents
Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof Download PDFInfo
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- CN112029149B CN112029149B CN202010974710.XA CN202010974710A CN112029149B CN 112029149 B CN112029149 B CN 112029149B CN 202010974710 A CN202010974710 A CN 202010974710A CN 112029149 B CN112029149 B CN 112029149B
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- soluble polymer
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- calcium carbonate
- polymer modifier
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 229920000728 polyester Polymers 0.000 title claims abstract description 25
- 239000003607 modifier Substances 0.000 title claims abstract description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 21
- 230000004048 modification Effects 0.000 title claims abstract description 18
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002715 modification method Methods 0.000 title description 2
- 150000002148 esters Chemical group 0.000 claims abstract description 19
- 238000012986 modification Methods 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 7
- 150000002009 diols Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 229910020491 K2TiF6 Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Chemical group OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- GZCKIUIIYCBICZ-UHFFFAOYSA-L disodium;benzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC(C([O-])=O)=C1 GZCKIUIIYCBICZ-UHFFFAOYSA-L 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 3
- 235000019463 artificial additive Nutrition 0.000 abstract description 2
- 238000009700 powder processing Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- -1 polyethylene terephthalate Polymers 0.000 description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000229 biodegradable polyester Polymers 0.000 description 2
- 239000004622 biodegradable polyester Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the field of inorganic powder processing and modifying synthetic additives, and particularly relates to a polyester water-soluble polymer modifier for calcium carbonate surface modification and a preparation method thereof. The modifier is prepared from the following raw materials in parts by mole: 1mol portion of dimethyl ester, 2.1mol portions of diol, 0.0001-0.001 mol portion of ester exchange catalyst and 0.0001-0.001 mol portion of polymerization catalyst; the modification has water solubility, the agent can reduce the oil absorption value of the heavy calcium powder, so that the high-value utilization of the heavy calcium powder is realized, and the preparation method has simple steps and low cost, and is suitable for industrial production.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of inorganic powder processing and modifying synthetic additives, and relates to a polyester water-soluble polymer modifier for calcium carbonate surface modification and a preparation method thereof.
[ background of the invention ]
Polyesters are a generic name for polymers obtained by polycondensation of polyhydric alcohols and polybasic acids, and are a very important class of high molecular materials. They can be classified into thermoplastic polyesters and thermosetting polyesters according to their behavior after heating, and into aromatic polyesters, aliphatic polyesters, alicyclic polyesters, etc. according to their molecular structures. Polyesters are widely used in various aspects of daily life, such as mineral water bottles (polyethylene terephthalate), clothing (dacron, polyethylene terephthalate), and the like. Particularly since the 21 st century, the sustainability of human production activities and the reduction of carbon dioxide gas emissions have attracted considerable attention, so that biodegradable polyesters have been developed vigorously, and some biodegradable polyesters excellent in overall performance, such as Polycaprolactone (PCL), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), have successively appeared and occupied a large share of the market, but they have a great disadvantage in price compared with polyolefins of comparable performance, and have restricted to some extent their faster and wider applications.
Calcium carbonate is an extremely important non-metallic mineral material, is widely applied to the fields of papermaking, plastics, rubber, coatings, papermaking, adhesives, foods, feeds and the like, and is expected to be low-carbon and economical in the face of the problems of excessive consumption of fossil resources, gradual severe environmental pollution and the like, and is upgraded to be a low-carbon material with high quality and low price.
However, the large differences in density and surface properties make calcium carbonate less than ideal for use in plastic, rubber, and the like articles. For this reason, a great deal of research and development efforts have focused on modifying the surface of calcium carbonate, mainly by chemical coating and assisted by mechanochemistry. The surface modifier used at present comprises stearic acid (salt), titanate coupling agent, aluminate coupling agent, atactic polypropylene, polyethylene wax and the like, the main purposes and effects of modification are mostly concentrated on reducing the oil absorption value and the like, the effect is single, the refinement is insufficient, and the modified powder is mainly applied to the field of polyolefin.
In order to expand the wider application of the biodegradable polymer, the cost is greatly reduced by high filling of calcium carbonate, which is a more effective way, however, how to ensure the better comprehensive performance of the composite material under the condition of high filling of calcium carbonate is a key problem in the industry commonality. Therefore, the research and development of the calcium carbonate surface macromolecular modifier special for the polyester is not slow, and no relevant research work is reported at present.
[ summary of the invention ]
The invention aims to provide a polyester water-soluble polymer modifier for calcium carbonate surface modification and a preparation method thereof, wherein the modifier has water solubility and can reduce the oil absorption value of heavy calcium powder so as to realize high-value utilization of the heavy calcium powder, the preparation method fully utilizes the characteristic of melt polycondensation, and sulfonic acid groups are introduced on a polyester macromolecular chain by virtue of dimethyl isophthalate-5-sodium sulfonate to regulate and control the water solubility of the product; in addition, the diol system can realize refined surface modification of calcium carbonate aiming at different polyester raw materials by introducing flexible chain segments such as polyethylene glycol, and the method has the advantages of simple steps and low cost, and is suitable for industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polyester water-soluble polymer modifier for calcium carbonate surface modification is prepared from the following raw materials in parts by mole: 1mol portion of dimethyl ester, 2.1mol portions of diol, 0.0001-0.001 mol portion of ester exchange catalyst and 0.0001-0.001 mol portion of polymerization catalyst.
Further, the dimethyl ester is a mixture of dimethyl terephthalate and dimethyl isophthalate-5-sodium sulfonate, and the mole ratio of the dimethyl terephthalate to the dimethyl isophthalate-5-sodium sulfonate is 0.97:0.03-0.5: 0.5.
Further, the diol is selected from one or more of ethylene glycol, propylene glycol, butanediol and polyethylene glycol.
Further, the transesterification catalyst is selected from antimony trioxide, tetra-n-butyl titanate or K2TiF6One kind of (1).
Further, the polymerization catalyst is selected from one of copper acetate, magnesium acetate or zinc acetate.
The preparation method of the polyester water-soluble polymer modifier for calcium carbonate surface modification comprises the following steps:
(1) ester exchange: mixing dimethyl ester, glycol and an ester exchange catalyst, placing the obtained mixture in a reactor with stirring, starting stirring, controlling the reaction temperature to be 140-205 ℃, and carrying out ester exchange reaction;
(2) polymerization: and (2) when the amount of the methanol evaporated in the step (1) is more than 1.6 times of that of the dimethyl ester, adding a polymerization catalyst, raising the temperature to 240-280 ℃, adjusting the vacuum degree to be below 40Pa, carrying out polycondensation reaction for 4-6 h, controlling the temperature to be 60-80 ℃ after the polycondensation is finished, and carrying out vacuum drying for 24-48 h to obtain the high-molecular modifier.
Further, the reactor is a three-neck flask or a stainless steel reaction kettle.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
compared with the prior art, the modifier prepared by the invention has water solubility, can reduce the oil absorption value of the heavy calcium powder, thereby realizing high-value utilization of the heavy calcium powder, and the preparation method fully utilizes the characteristics of melt polycondensation, introduces sulfonic acid groups on a polyester macromolecular chain by virtue of dimethyl isophthalate-5-sodium sulfonate, and can regulate and control the water solubility of the product; in addition, the diol system can realize refined surface modification of calcium carbonate aiming at different polyester raw materials by introducing flexible chain segments such as polyethylene glycol, and the method has the advantages of simple steps and low cost, and is suitable for industrial production.
[ detailed description ] embodiments
The invention will now be further illustrated by reference to the following examples.
Example 1
(1) Adding 0.97mol of dimethyl terephthalate, 0.03mol of dimethyl isophthalate-5-sodium sulfonate, 2.1mol of ethylene glycol and 0.0001mol of n-tetrabutyl titanate into a 500ml three-neck flask with mechanical stirring, and controlling the reaction temperature to be 140 ℃ for ester exchange;
(2) adding 0.0001mol of zinc acetate after the amount of methanol evaporated by ester exchange reaches 65.5ml, controlling the temperature to 240 ℃, carrying out polycondensation reaction for 4h under the pressure of less than 40Pa, and carrying out vacuum drying for 24h at 80 ℃ after polycondensation reaction to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by 1% aqueous solution of the product are measured.
Example 2
(1) Adding 0.90mol of dimethyl terephthalate, 0.10mol of dimethyl isophthalate-5-sodium sulfonate, 2.1mol of propylene glycol and 0.0005mol of antimony trioxide into a 500ml three-neck flask with mechanical stirring, and controlling the reaction temperature to be 160 ℃ for ester exchange;
(2) and (3) after the methanol amount evaporated by ester exchange reaches 65.5ml, adding 0.0005mol of copper acetate, controlling the temperature to be 240 ℃, carrying out polycondensation reaction for 4h under the pressure of less than 40Pa, and carrying out vacuum drying for 24h at 80 ℃ after polycondensation reaction to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by 1% aqueous solution of the product are measured.
Example 3
(1) Adding 0.80mol of dimethyl terephthalate, 0.20mol of dimethyl isophthalate-5-sodium sulfonate, 2.1mol of butanediol and 0.0007mol of K2TiF6 into a 500ml three-neck flask with mechanical stirring, and controlling the reaction temperature to be 180 ℃ for ester exchange;
(2) after the methanol amount distilled out by ester exchange reaches 65.5ml, 0.0007mol of magnesium acetate is added, the temperature is controlled to be 240 ℃, the polycondensation reaction is carried out for 4h under the pressure of less than 40Pa, and the product is obtained after the polycondensation reaction is carried out for 24h under the vacuum drying at the temperature of 80 ℃. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by 1% aqueous solution of the product are measured.
Example 4
(1) Adding 0.50mol of dimethyl terephthalate, 0.50mol of dimethyl isophthalate-5-sodium sulfonate, 2.1mol of butanediol and 0.001mol of tetra-n-butyl titanate into a 500ml three-neck flask with mechanical stirring, and controlling the reaction temperature to be 205 ℃ for ester exchange;
(2) adding 0.001mol of zinc acetate after the amount of methanol evaporated by ester exchange reaches 65.5ml, controlling the temperature at 280 ℃, carrying out polycondensation reaction for 4h under the pressure of less than 40Pa, and carrying out vacuum drying for 24h at 80 ℃ after polycondensation reaction to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by 1% aqueous solution of the product are measured.
Example 5:
(1) adding 0.70mol of dimethyl terephthalate, 0.30mol of dimethyl isophthalate-5-sodium sulfonate, 2.0mol of butanediol, 0.1mol of polyethylene glycol (with a weight average molecular weight of 2000g/mol) and 0.001mol of tetra-n-butyl titanate into a stainless steel reaction kettle which is provided with a mechanical stirrer and has a volume of 1L, and controlling the reaction temperature to be 160 ℃ for ester exchange;
(2) adding 0.001mol of zinc acetate after the amount of methanol evaporated by ester exchange reaches 65.5ml, controlling the temperature to be 260 ℃, carrying out polycondensation reaction for 4h under the pressure of less than 40Pa, and carrying out vacuum drying for 24h at 80 ℃ after polycondensation reaction to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by 1% aqueous solution of the product are measured. The values are given in Table 1.
TABLE 1
The test methods used by the performance indexes are respectively as follows:
molecular weight test used was Gel Permeation Chromatography (GPC): the instrument used was ALC-GPC (high temperature high pressure gel permeation chromatograph at 150 ℃ C.) from Waters corporation, USA; a mixed solvent of phenol and tetrachloroethane (the weight ratio is 1:1) is used as a solvent; chloroform and 1% absolute ethyl alcohol are used as eluent; time: 25 minutes; flow rate: 1.0 mL/min; sample introduction amount: 150 ul; column Chamber temperature: 30 ℃; sample chamber temperature: 30 ℃; pump chamber temperature: at 30 ℃.
The method for measuring the solubility comprises the following steps: the equilibrium method comprises accurately weighing 10g of water-soluble polymer modifier, adding into 100g of deionized water, stirring at constant temperature of 25 deg.C for 5min, standing, and analyzing the composition of the upper layer solution to obtain the solubility at the temperature.
The method for measuring the oil absorption value comprises the following steps: accurately weighing 5g of activated calcium carbonate product, placing the calcium carbonate product on a glass plate, dripping DOP (dioctyl phthalate) (DOP) into a dropping bottle with known weight, continuously turning and grinding by using a knife, dispersing a sample initially, gradually agglomerating until the sample is completely infiltrated by the DOP, and forming an integral agglomerate as a terminal point, and accurately weighing the mass of the dropping bottle. The oil absorption value is expressed as the mass fraction of DOP absorbed per 100g of calcium carbonate.
The foregoing description of the embodiments is provided to facilitate an understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. The application of polyester water-soluble polymer modifier in calcium carbonate surface modification is characterized by that,
the polyester water-soluble polymer modifier is prepared from the following raw materials in parts by mole: 1mol portion of dimethyl ester, 2.1mol portions of diol, 0.0001-0.001 mol portion of ester exchange catalyst and 0.0001-0.001 mol portion of polymerization catalyst; the dimethyl ester is a mixture of dimethyl terephthalate and dimethyl isophthalate-5-sodium sulfonate, and the mole ratio of the dimethyl ester to the sodium isophthalate is 0.97:0.03-0.5: 0.5;
the preparation method of the polyester water-soluble polymer modifier comprises the following steps:
(1) ester exchange: mixing dimethyl ester, glycol and an ester exchange catalyst, placing the obtained mixture in a reactor with stirring, starting stirring, controlling the reaction temperature to be 140-205 ℃, and carrying out ester exchange reaction;
(2) polymerization: and (2) when the amount of the methanol evaporated in the step (1) is more than 1.6 times of that of the dimethyl ester, adding a polymerization catalyst, raising the temperature to 240-280 ℃, adjusting the vacuum degree to be below 40Pa, carrying out polycondensation reaction for 4-6 h, controlling the temperature to be 60-80 ℃ after the polycondensation is finished, and carrying out vacuum drying for 24-48 h to obtain the high-molecular modifier.
2. The use of the polyester-based water-soluble polymer modifier for surface modification of calcium carbonate according to claim 1, wherein the glycol is one or more selected from ethylene glycol, propylene glycol, butylene glycol and polyethylene glycol.
3. The use of the polyester-based water-soluble polymer modifier according to claim 1 for surface modification of calcium carbonateCharacterized in that the transesterification catalyst is selected from antimony trioxide, tetra-n-butyl titanate or K2TiF6One kind of (1).
4. The use of the polyester-based water-soluble polymer modifier for surface modification of calcium carbonate according to claim 1, wherein the polymerization catalyst is one selected from copper acetate, magnesium acetate and zinc acetate.
5. The use of the polyester-based water-soluble polymer modifier according to claim 1 for surface modification of calcium carbonate, wherein the reactor is a three-necked flask or a stainless steel reaction vessel.
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| KR100616188B1 (en) * | 2000-07-26 | 2006-08-25 | 주식회사 휴비스 | Polyester copolymer and preparation thereof |
| JP4225107B2 (en) * | 2003-05-08 | 2009-02-18 | 東レ株式会社 | Water-soluble polyester composition |
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Application publication date: 20201204 Assignee: Guangxi Hezhou Asia Pacific powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046438 Denomination of invention: A polyester type water-soluble polymer modifier for surface modification of calcium carbonate and its preparation method Granted publication date: 20220218 License type: Common License Record date: 20231108 Application publication date: 20201204 Assignee: Guangxi Hezhou Kewei New Material Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046408 Denomination of invention: A polyester type water-soluble polymer modifier for surface modification of calcium carbonate and its preparation method Granted publication date: 20220218 License type: Common License Record date: 20231108 Application publication date: 20201204 Assignee: Guangxi Hezhou Jinlong Powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046406 Denomination of invention: A polyester type water-soluble polymer modifier for surface modification of calcium carbonate and its preparation method Granted publication date: 20220218 License type: Common License Record date: 20231108 Application publication date: 20201204 Assignee: Hezhou Xinhua hair powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046344 Denomination of invention: A polyester type water-soluble polymer modifier for surface modification of calcium carbonate and its preparation method Granted publication date: 20220218 License type: Common License Record date: 20231108 Application publication date: 20201204 Assignee: Hezhou Guangli powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046341 Denomination of invention: A polyester type water-soluble polymer modifier for surface modification of calcium carbonate and its preparation method Granted publication date: 20220218 License type: Common License Record date: 20231108 Application publication date: 20201204 Assignee: Hezhou Fuyuan Powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046335 Denomination of invention: A polyester type water-soluble polymer modifier for surface modification of calcium carbonate and its preparation method Granted publication date: 20220218 License type: Common License Record date: 20231108 Application publication date: 20201204 Assignee: Hezhou Zhaojun Chemical Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046442 Denomination of invention: A polyester type water-soluble polymer modifier for surface modification of calcium carbonate and its preparation method Granted publication date: 20220218 License type: Common License Record date: 20231108 |