CN112375218B - Water-soluble polymer modifier containing nylon structure for calcium carbonate surface modification and preparation method thereof - Google Patents
Water-soluble polymer modifier containing nylon structure for calcium carbonate surface modification and preparation method thereof Download PDFInfo
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- CN112375218B CN112375218B CN202010976265.0A CN202010976265A CN112375218B CN 112375218 B CN112375218 B CN 112375218B CN 202010976265 A CN202010976265 A CN 202010976265A CN 112375218 B CN112375218 B CN 112375218B
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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 67
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 33
- 239000003607 modifier Substances 0.000 title claims abstract description 21
- 239000004677 Nylon Substances 0.000 title claims abstract description 17
- 230000004048 modification Effects 0.000 title claims abstract description 17
- 229920001778 nylon Polymers 0.000 title claims abstract description 17
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000002715 modification method Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 15
- 150000001450 anions Chemical group 0.000 claims abstract 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- GEBIBHFITVKXGW-UHFFFAOYSA-N 3-(1-aminobutyl)aziridin-2-one Chemical compound CCCC(N)C1NC1=O GEBIBHFITVKXGW-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 claims description 7
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 claims description 6
- REJHVSOVQBJEBF-UHFFFAOYSA-N DSD-acid Natural products OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 claims description 3
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
- 150000004678 hydrides Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011575 calcium Substances 0.000 abstract description 17
- 229910052791 calcium Inorganic materials 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 235000019463 artificial additive Nutrition 0.000 abstract description 2
- 238000009700 powder processing Methods 0.000 abstract description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- -1 coatings Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920006052 Chinlon® 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
- 229920004933 Terylene® Polymers 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
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 238000011161 development Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 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
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor 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
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- 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
- 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
Abstract
The invention belongs to the field of inorganic powder processing and modifying synthetic additives, and particularly relates to a water-soluble polymer modifier containing a nylon structure and used for calcium carbonate surface modification and a preparation method thereof. The modifier is prepared by introducing a compound shown in formula 1 onto a nylon macromolecular chain by means of anion ring-opening polymerization; the modifier can reduce the oil absorption value of the heavy calcium powder, endow the heavy calcium powder with antibacterial performance, improve the whiteness of the heavy calcium powder, reduce the dust pollution of the heavy calcium powder, improve the interface compatibility between the heavy calcium powder and a polymer and the like, so that the high-value utilization of the heavy calcium powder is realized.
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 water-soluble polymer modifier containing a nylon structure and used for calcium carbonate surface modification and a preparation method thereof.
[ background of the invention ]
Calcium carbonate is an extremely important nonmetallic mineral material, and is the first country for producing calcium carbonate in China, the annual output is nearly 3000 ten thousand tons at present, and the calcium carbonate is widely applied to the fields of papermaking, plastics, rubber, coatings, adhesives, foods, feeds and the like. In the face of the problems of excessive consumption of fossil resources, increasingly serious environmental pollution and the like, low-carbon economy is demanded, and calcium carbonate is promoted to be a low-carbon material with high quality and low price.
However, the large difference in density and surface properties makes the calcium carbonate less desirable for use in articles such as plastics, rubber, etc., especially when the calcium carbonate loading is high (above 50 wt.%) with a dramatic decrease in the processability and overall performance of the composite. For this reason, a great deal of research and development efforts have focused on modifying the surface of calcium carbonate to improve and control the interfacial compatibility between calcium carbonate and organic polymers, and the modification method is mainly chemical coating assisted by mechanochemistry. The currently used surface modifiers comprise stearic acid (salt), titanate coupling agent, aluminate coupling agent, atactic polypropylene, polyethylene wax and the like, the main purpose and effect of modification are mostly concentrated on reducing oil absorption value and the like, the effect is single, refinement is insufficient, and the added value of products is low.
The high polymer material is widely applied to the fields of clothes (such as terylene and chinlon), daily necessities and the like, is also one of the main application fields of calcium carbonate, changes the traditional volume filler of calcium carbonate into functional filler by virtue of the advantages of large calcium carbonate amount, high quality and low price, has extremely important practical significance for the development of high-performance polymer matrix composite materials, and is expected to have wide market prospect.
[ summary of the invention ]
The invention aims to provide a water-soluble polymer modifier containing a nylon structure and used for calcium carbonate surface modification and a preparation method thereof, wherein the modifier can reduce the oil absorption value of heavy calcium carbonate powder, endow the heavy calcium carbonate powder with antibacterial performance, improve the whiteness of the heavy calcium carbonate powder, reduce the dust pollution of the heavy calcium carbonate powder, improve the interface compatibility between the heavy calcium carbonate powder and a polymer and the like, so that the high-value utilization of the heavy calcium carbonate powder is realized, and the preparation method has the advantages of simple steps, low cost and suitability for industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a water-soluble polymer modifier containing a nylon structure and used for surface modification of calcium carbonate is prepared by introducing a compound shown in a formula 1 onto a nylon macromolecular chain through anionic ring-opening polymerization;
wherein, in the formula 1,
r1 (H) is selected from one of alkylamine;
r2 (H) is 3-amino-2-caprolactam.
Preferably, R1 (H) is selected from one of N, N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine.
Further, the compound represented by the formula 1 is prepared according to the following steps:
step 1: adding 2 parts of cyanuric chloride by mole into 1 part of 4,4 '-diaminostilbene-2,2' -disulfonic acid aqueous solution by mole, stirring at 0-5 ℃, and continuously dropwise adding 1mol/l sodium hydroxide solution to keep the pH value at 4-5 for reaction for 2 hours;
step 2: raising the temperature to 40-50 ℃, dropwise adding 2 parts of N, N-dimethyldodecylamine or N, N-dimethyltetradecylamine or N, N-dimethylhexadecylamine with molar number into the system obtained after the reaction in the step 1, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 6-7, and stirring for reacting for 4 hours;
and 3, step 3: adding 2 parts by mole of 3-amino-2-caprolactam into the solution obtained in the step 2, heating the reaction mixture to reflux, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 8-9, and stirring for reacting for 6 hours;
and 4, step 4: and (3) cooling the mixture obtained in the step (3) to room temperature, adding 3mol/l of hydrochloric acid aqueous solution to reach the pH value of 2.7-3.3, separating out crystals, washing with distilled water and drying to obtain the compound shown in the formula 1.
The preparation method of the water-soluble polymer modifier containing the nylon structure and used for calcium carbonate surface modification comprises the following steps:
mixing 5-10 parts by weight of a compound shown as a formula 1 and 90-95 parts by weight of lactam to obtain a mixture, adding a catalyst accounting for 0.2-1% of the total weight of the mixture, carrying out reduced pressure distillation at 110-160 ℃ for 10-30 min, removing trace water, adding an activator accounting for 0.2-1% of the total weight of the mixture, quickly shaking up, and immediately pouring into a preheated mold at 140-180 ℃ for polymerization for 20-70 min to obtain the catalyst.
Further, the lactam is selected from one of caprolactam, enantholactam, capryllactam and laurolactam.
Further, the catalyst is selected from one of alkali metal, alkali metal hydride and alkali metal hydroxide.
Further, the activating agent is selected from one of toluene-2,4-diisocyanate (TDI) and N, N' -Dicyclohexylcarbodiimide (DCC).
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 can reduce the oil absorption value of the heavy calcium powder, endow the heavy calcium powder with antibacterial performance, improve the whiteness of the heavy calcium powder, reduce the dust pollution of the heavy calcium powder, improve the interface compatibility between the heavy calcium powder and a polymer and the like, thereby realizing the high-value utilization of the heavy calcium powder.
[ detailed description ] embodiments
The invention will now be further illustrated by reference to the following examples.
Example 1
(1) Adding 2 parts of cyanuric chloride by mole into 1 part of 4,4 '-diaminostilbene-2,2' -disulfonic acid aqueous solution by mole, stirring at 0-5 ℃, and continuously dropwise adding 1mol/l sodium hydroxide solution to keep the pH value at 4-5 for reaction for 2 hours;
(2) Raising the temperature to 40-50 ℃, dropwise adding 2 parts of N, N-dimethyldodecylamine solution with mole number into the system obtained after the reaction in the step 1, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 6-7, and stirring for reaction for 4 hours;
(3) Adding 2 parts by mole of 3-amino-2-caprolactam into the solution obtained in the step 2, heating the reaction mixture to reflux, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 8-9, and stirring for reacting for 6 hours;
(4) And (4) cooling the mixture obtained in the step (3) to room temperature, adding 3mol/l hydrochloric acid aqueous solution to keep the pH value at 3, separating out crystals, washing with distilled water and drying to obtain the compound shown in the formula 1.
Wherein, in formula 1, R 1 (H) Is N, N-dimethyldodecylamine; r 2 (H) Is 3-amino-2-caprolactam;
(5) Mixing 5 parts by weight of a compound shown as a formula 1 and 95 parts by weight of caprolactam, adding sodium hydroxide accounting for 0.2 percent of the total weight of the mixture, carrying out reduced pressure distillation at 120 ℃ for 30min, removing trace water, adding toluene-2,4-diisocyanate accounting for 1 percent of the total weight of the mixture, quickly shaking up, immediately pouring into a preheated mold at 150 ℃ for polymerization for 20min to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by the 1% aqueous solution are tested, and the results are shown in Table 1.
Example 2
(1) Adding 2 parts of cyanuric chloride by mole into 1 part of 4,4 '-diaminostilbene-2,2' -disulfonic acid aqueous solution by mole, stirring at 0-5 ℃, and continuously dropwise adding 1mol/l sodium hydroxide solution to keep the pH value at 4-5 for reaction for 2 hours;
(2) Raising the temperature to 40-50 ℃, dropwise adding 2 parts of N, N-dimethyltetradecylamine solution with mole number into the system obtained after the reaction in the step 1, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 6-7, and stirring for reaction for 4 hours;
(3) Adding 2 parts by mole of 3-amino-2-caprolactam into the solution obtained in the step 2, heating the reaction mixture to reflux, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 8-9, and stirring for reacting for 6 hours;
(4) And (3) cooling the mixture obtained in the step (3) to room temperature, adding 3mol/l hydrochloric acid aqueous solution to keep the pH value at 2.7, separating out crystals, washing with distilled water and drying to obtain the compound shown in the formula 1.
Wherein, in formula 1, R 1 (H) Is N, N-dimethyltetradecylamine; r 2 (H) Is 3-amino-2-caprolactam;
(5) Mixing 10 parts by weight of compound shown in formula 1 and 90 parts by weight of enantholactam, adding 1 percent of sodium hydroxide in the total weight of the mixture, carrying out reduced pressure distillation at 140 ℃ for 20min, removing trace water, adding toluene-2,4-diisocyanate which is 0.7 percent of the total weight of the mixture, quickly shaking up, immediately pouring into a preheated mold at 160 ℃ for polymerization for 40min to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by the 1% aqueous solution are tested, and the results are shown in Table 1.
Example 3
(1) Adding 2 parts of cyanuric chloride by mole into an aqueous solution containing 1 part of 4,4 '-diaminostilbene-2,2' -disulfonic acid by mole, stirring at 0-5 ℃, and continuously dropwise adding 1mol/l sodium hydroxide solution to keep the pH value to react for 2 hours under the condition of 4-5;
(2) Raising the temperature to 40-50 ℃, dropwise adding 2 parts of N, N-dimethylhexadecylamine solution with mole number into the system obtained after the reaction in the step 1, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 6-7, and stirring for reacting for 4 hours;
(3) Adding 2 parts by mole of 3-amino-2-caprolactam into the solution obtained in the step 2, heating the reaction mixture to reflux, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 8-9, and stirring for reacting for 6 hours;
(4) And (3) cooling the mixture obtained in the step (3) to room temperature, adding 3mol/l hydrochloric acid aqueous solution to keep the pH value at 3.3, separating out crystals, washing with distilled water and drying to obtain the compound shown in the formula 1.
Wherein, in formula 1, R 1 (H) Is N, N-dimethylhexadecylamine; r 2 (H) Is 3-amino-2-caprolactam;
(5) Mixing 7 parts by weight of a compound shown as a formula 1 and 93 parts by weight of caprylolactam, adding sodium hydroxide accounting for 0.9 percent of the total weight of the mixture, carrying out reduced pressure distillation at 160 ℃ for 20min, removing trace water, adding N, N' -dicyclohexylcarbodiimide accounting for 0.2 percent of the total weight of the mixture, quickly shaking up, immediately pouring into a preheated mold at 170 ℃ and carrying out polymerization for 60min to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by the 1% aqueous solution are tested, and the results are shown in Table 1.
Example 4
(1) Adding 2 parts of cyanuric chloride by mole into 1 part of 4,4 '-diaminostilbene-2,2' -disulfonic acid aqueous solution by mole, stirring at 0-5 ℃, and continuously dropwise adding 1mol/l sodium hydroxide solution to keep the pH value at 4-5 for reaction for 2 hours;
(2) Raising the temperature to 40-50 ℃, dropwise adding 2 parts of N, N-dimethylhexadecylamine solution with mole number into the system reacted in the step 1, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 6-7, and stirring for reaction for 4 hours;
(3) Adding 2 parts by mole of 3-amino-2-caprolactam into the solution obtained in the step 2, heating the reaction mixture to reflux, continuously dropwise adding 1mol/l of sodium hydroxide solution to keep the pH value at 8-9, and stirring for reacting for 6 hours;
(4) And (3) cooling the mixture obtained in the step (3) to room temperature, adding 3mol/l hydrochloric acid aqueous solution to keep the pH value at 2.9, separating out crystals, washing with distilled water and drying to obtain the compound shown in the formula 1.
Wherein, in formula 1, R 1 (H) Is N, N-dimethylhexadecylamine; r 2 (H) Is 3-amino-2-caprolactam;
(5) Mixing 10 parts by weight of a compound shown as a formula 1 and 90 parts by weight of laurolactam, adding potassium hydroxide accounting for 1 percent of the total weight of the mixture, carrying out reduced pressure distillation at 150 ℃ for 10min, removing trace water, adding N, N' -dicyclohexylcarbodiimide accounting for 1 percent of the total weight of the mixture, quickly shaking up, immediately pouring into a preheated mold at 155 ℃ to polymerize for 70min to obtain the product. The molecular weight, water solubility and oil absorption value of the 1500-mesh heavy calcium powder modified by the 1% aqueous solution are tested, and the results are shown in Table 1.
TABLE 1
| Example (b) | Weight average molecular weight (ten thousand) | Solubility (25 ℃,100 g water) | Oil absorption value (unmodified 1500 mesh heavy calcium powder oil absorption value is 28) |
| Example 1 | 1.75 | 2.3 | 24 |
| Example 2 | 1.07 | 5 | 18 |
| Example 3 | 1.45 | 3.5 | 22 |
| Example 4 | 0.96 | 5.3 | 17 |
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: 1.0mL/min; sample injection amount: 150ul; 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 ℃ for 5min, and analyzing the composition of the upper solution after standing 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 (7)
1. A water-soluble polymer modifier containing a nylon structure and used for surface modification of calcium carbonate is characterized in that the modifier is prepared by introducing a compound shown as a formula 1 onto a nylon macromolecular chain by means of anion ring-opening polymerization;
wherein, in the formula 1,
r1 is alkylamino;
r2 is 3-amino-2-caprolactam radical.
2. The water-soluble polymer modifier for calcium carbonate surface modification containing a nylon structure according to claim 1, characterized in that: r1 is selected from one of N, N-dimethyl dodecyl amino, N-dimethyl tetradecyl amino and N, N-dimethyl hexadecyl amino.
3. The water-soluble polymer modifier for calcium carbonate surface modification containing a nylon structure according to claim 1 or 2, wherein the compound represented by formula 1 is prepared by the following steps:
step 1: adding 2 parts of cyanuric chloride by mole into 1 part of 4,4 '-diaminostilbene-2,2' -disulfonic acid aqueous solution by mole, stirring at 0-5 ℃, and continuously dropwise adding 1mol/L sodium hydroxide solution to keep the pH value at 4-5 for reaction for 2 hours;
step 2: raising the temperature to 40-50 ℃, dropwise adding 2 parts of N, N-dimethyldodecylamine or N, N-dimethyltetradecylamine or N, N-dimethylhexadecylamine with molar number into the system obtained after the reaction in the step 1, continuously dropwise adding 1mol/L sodium hydroxide solution to keep the pH value at 6-7, and stirring for reacting for 4 hours;
and step 3: adding 2 parts by mole of 3-amino-2-caprolactam into the solution obtained in the step 2, heating the reaction mixture to reflux, continuously dropwise adding 1mol/L sodium hydroxide solution to keep the pH value at 8-9, and stirring for reacting for 6 hours;
and 4, step 4: and (3) cooling the mixture obtained in the step (3) to room temperature, adding 3mol/L hydrochloric acid aqueous solution to reach the pH value of 2.7-3.3, separating out crystals, washing with distilled water and drying to obtain the compound shown in the formula 1.
4. The method for preparing the water-soluble polymer modifier containing a nylon structure for calcium carbonate surface modification according to any one of claims 1 to 3, characterized by comprising the steps of:
mixing 5-10 parts by weight of a compound shown as a formula 1 and 90-95 parts by weight of lactam to obtain a mixture, adding a catalyst accounting for 0.2-1% of the total weight of the mixture, carrying out reduced pressure distillation at 110-160 ℃ for 10-30 min, removing trace water, adding an activator accounting for 0.2-1% of the total weight of the mixture, quickly shaking up, and immediately pouring into a preheated mold at 140-180 ℃ for polymerization for 20-70 min to obtain the catalyst.
5. The method for preparing the water-soluble polymer modifier with nylon structure for calcium carbonate surface modification according to claim 4, wherein the lactam is one selected from caprolactam, enantholactam, caprylolactam and laurolactam.
6. The method for preparing the water-soluble polymer modifier containing a nylon structure for calcium carbonate surface modification according to claim 4, wherein the catalyst is one selected from alkali metals, hydrides of alkali metals and hydroxides of alkali metals.
7. The method for preparing the water-soluble polymer modifier containing a nylon structure for calcium carbonate surface modification according to claim 4, wherein the activating agent is one selected from toluene-2,4-diisocyanate (TDI), and N, N' -Dicyclohexylcarbodiimide (DCC).
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Application publication date: 20210219 Assignee: Guangxi Hezhou Asia Pacific powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046438 Denomination of invention: A water-soluble polymer modifier containing nylon structure for surface modification of calcium carbonate and its preparation method Granted publication date: 20221028 License type: Common License Record date: 20231108 Application publication date: 20210219 Assignee: Guangxi Hezhou Kewei New Material Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046408 Denomination of invention: A water-soluble polymer modifier containing nylon structure for surface modification of calcium carbonate and its preparation method Granted publication date: 20221028 License type: Common License Record date: 20231108 Application publication date: 20210219 Assignee: Guangxi Hezhou Jinlong Powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046406 Denomination of invention: A water-soluble polymer modifier containing nylon structure for surface modification of calcium carbonate and its preparation method Granted publication date: 20221028 License type: Common License Record date: 20231108 Application publication date: 20210219 Assignee: Hezhou Xinhua hair powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046344 Denomination of invention: A water-soluble polymer modifier containing nylon structure for surface modification of calcium carbonate and its preparation method Granted publication date: 20221028 License type: Common License Record date: 20231108 Application publication date: 20210219 Assignee: Hezhou Guangli powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046341 Denomination of invention: A water-soluble polymer modifier containing nylon structure for surface modification of calcium carbonate and its preparation method Granted publication date: 20221028 License type: Common License Record date: 20231108 Application publication date: 20210219 Assignee: Hezhou Fuyuan Powder Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046335 Denomination of invention: A water-soluble polymer modifier containing nylon structure for surface modification of calcium carbonate and its preparation method Granted publication date: 20221028 License type: Common License Record date: 20231108 Application publication date: 20210219 Assignee: Hezhou Zhaojun Chemical Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046442 Denomination of invention: A water-soluble polymer modifier containing nylon structure for surface modification of calcium carbonate and its preparation method Granted publication date: 20221028 License type: Common License Record date: 20231108 |
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