CN106046316A - Preparation method of low-density crosslinked tree-like branched cationic polysiloxane micro-emulsion and product thereof - Google Patents
Preparation method of low-density crosslinked tree-like branched cationic polysiloxane micro-emulsion and product thereof Download PDFInfo
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- CN106046316A CN106046316A CN201610361752.XA CN201610361752A CN106046316A CN 106046316 A CN106046316 A CN 106046316A CN 201610361752 A CN201610361752 A CN 201610361752A CN 106046316 A CN106046316 A CN 106046316A
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- tree
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 141
- -1 polysiloxane Polymers 0.000 title claims abstract description 84
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 80
- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000004132 cross linking Methods 0.000 claims abstract description 69
- 239000004970 Chain extender Substances 0.000 claims abstract description 56
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 49
- 239000013638 trimer Substances 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000004945 emulsification Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 111
- 239000003085 diluting agent Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 37
- 150000001768 cations Chemical group 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 229920002521 macromolecule Polymers 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000002671 adjuvant Substances 0.000 claims description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000001804 emulsifying effect Effects 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 230000004044 response Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008234 soft water Substances 0.000 claims description 5
- ZHUWIYQJHBMTCY-UHFFFAOYSA-N 3-[ethoxy(2,2,2-triethoxyethoxy)silyl]propan-1-amine Chemical compound NCCC[SiH](OCC(OCC)(OCC)OCC)OCC ZHUWIYQJHBMTCY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical group 0.000 claims 1
- 239000004753 textile Substances 0.000 abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 5
- 239000004902 Softening Agent Substances 0.000 description 26
- 229920000570 polyether Polymers 0.000 description 21
- 239000004721 Polyphenylene oxide Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000000159 acid neutralizing agent Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009965 tatting Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 229920013822 aminosilicone Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229960002725 isoflurane Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical group CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical group CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
Abstract
The invention relates to a preparation method of a low-density crosslinked tree-like branched cationic polysiloxane micro-emulsion and a product thereof. The preparation method includes the following steps that raw materials are prepared; a middle-poly-w-alkyl polysiloxane linear body is subjected to dehydration pretreatment; the middle-poly-w-alkyl polysiloxane linear body subjected to dehydration pretreatment performs preliminary polymerization reaction with parts of diisocyanate and a polymerization catalyst to prepare a preliminary polymerization body; the preliminary polymerization body reacts with a non-ionic chain extender, a diisocyanate trimer and residual diisocyanate to prepare a prepolymer; the prepolymer reacts with the cationic chain extender and parts of a thinner to prepare an intermediate; the intermediate reacts with a silane coupling agent for termination; emulsification is performed to obtain the micro-emulsion. The product of the low-density crosslinked tree-like branched cationic polysiloxane micro-emulsion has higher-density branched polysiloxane long chains and cationic groups, meanwhile has a certain-density crosslinking structure and can remarkably improve the high-elasticity smooth hand feeling of all types of woven and textile products.
Description
Technical field
The present invention relates to the polysiloxane microemulsion that the high-elastic soft and smooth feel style of all kinds of textile product arranges, be specifically related to
Preparation method of tree-shaped cladodification cationic silicone microemulsion a kind of of low-density crosslinking and products thereof.
Background technology
At field of textiles, organosilicon macromolecule emulsion is commonly used for the soft style of various textile product and arranges.At present, spin
Knitting the soft finish of product normally used is polyether-modified hydrophilic organic silicon macromolecule softening agent product or amino modified
Organosilicon macromolecule softening agent product, its feel all presents preferable flexibility and lacks flexibility and slide sense.For solving tradition
Silicone softening agent product lacks flexibility and the problem of sliding sense, the various modified high-moleculars with polysiloxanes as essential building blocks
Emulsion usually used as additive application in tradition organosilicon macromolecule softening agent product in.These modified high-moleculars generally by
Block, it is grafted and various polysiloxane structure unit are introduced modified high-molecular skeleton, end or side by the chemical method such as end-blocking,
Carry out again emulsion dispersion process prepare.
Above-mentioned raw materials can be classified as being polymerized monomer, modifying agent, adjuvant and water, wherein: polymerization monomer includes organic siloxane
Ring body, organosiloxane linear body, hydrogeneous organosiloxane ring body, hydrogeneous organosiloxane linear body, hydroxyl polysiloxane, end
Hydroxyl alkyl polysiloxanes, amino silicane coupling agent, polyethers amino silicane coupling agent, active polyether；Modifying agent be quaternizing agent,
Epoxy compounds, diisocyanate, PEPA, polyether polyol, polyolefin polyhydric alcohol, cation chain extender, non-from
Sub-chain extender；Adjuvant includes polymerization catalyst, nertralizer, diluent.
The preparation method of the modified high-molecular of organosilicon macromolecule softening agent and silicone matrix includes following several at present
Kind:
1, the preparation method of polyether block modified amido silicone softening agent, its raw material include be polymerized monomer, modifying agent,
Adjuvant and distilled water, wherein: polymerization monomer includes hydroxyl polysiloxane, active polyether；Modifying agent is epoxy compounds；Auxiliary
Auxiliary agent includes polymerization catalyst, nertralizer and diluent.
As written by Hao Kuiyuan, Wang Shugen, Su Kai " synthesis of polyether block amino-modified silicone smooth agent and application "
The preparation method of polyether block modified amido silicone softening agent disclosed in (" printing and dyeing assistant " the 12nd phases of volume 29 in 2012), it
In raw material: polymerization monomer is both-end hydroxyl polysiloxane, double-end amino polyethers；Modifying agent is epoxychloropropane；Adjuvant is for urging
Agent anhydrous stannic chloride and sodium hydroxide, nertralizer acetic acid, diluent isopropanol and toluene；Emulsification is distilled water.
Although the amino of the polyether block hydrophilic modifying amino-silicone oil softening agent that the method is prepared and polyethers chain link are all located
In softening agent molecular backbone structure, but its amino content is relatively low, cationic is more weak, the absorption to fiber of the softening agent molecule
Ability and the poor-performing of tolerance technique for applying conditional fluctuation.Simultaneously, although softening agent macromolecule has certain chemism,
But macromole lacks high degree of grafting.Therefore, this softening agent gives feel style and the Conventional amino silicone oil or polyether-modified of fabric
The soft style and features of hydrophilic amino silicone oil softening agent product is as broad as long, hence it is evident that the soft style lacking " high-elastic soft cunning " is special
Levy.
2, the preparation method of polyether block modified amido silicone softening agent, its raw material include be polymerized monomer, modifying agent,
Adjuvant and distilled water, wherein: polymerization monomer includes hydrogeneous organosilicon linear body, active polyether；Modifying agent is epoxy radicals chemical combination
Thing；Adjuvant includes polymerization catalyst, nertralizer, diluent.
As written by Zhu Yanhong, Qian Cheng, Zhou great Peng et al. " structural characterization of block type Polyether/amino-modified Silicone and application performance "
The preparation method of polyether block modified amido silicone softening agent disclosed in (" textile journal " the 4th phases of volume 32 in 2011), it
In raw material: polymerization monomer is end containing hydrogen silicone oil, amine terminated polyether；Modifying agent is allyl glycidyl ether；Adjuvant is self-control
Platinum catalyst, nertralizer acetic acid, diluent isopropanol；Emulsification is distilled water.
Identical with front, although the amino of polyether block hydrophilic modifying amino-silicone oil softening agent prepared of the method and polyethers
Chain link is in softening agent molecular backbone structure, but its amino access amount is relatively low, the therefore softening agent molecule suction to fiber
Attached ability and the poor-performing of tolerance technique for applying conditional fluctuation.Meanwhile, macromole lacks high degree of grafting.Therefore, this softening agent
Give feel style and Conventional amino silicone oil or the soft style of polyether-modified hydrophilic amino silicone oil softening agent product of fabric
Feature is as broad as long, hence it is evident that lack the soft style and features of " high-elastic soft cunning ".
3, the preparation method of the organic-silicon-modified cation aqueous polyurethane of response type, its raw material includes being polymerized monomer, changing
Property agent, adjuvant and distilled water, wherein: polymerization monomer includes hydroxyl alkyl-terminated polysiloxane, amino silicane coupling agent；Modifying agent bag
Include polyolefin polyhydric alcohol, diisocyanate, cation chain extender, nonionic chain extender；Adjuvant includes quaternizing agent, neutralization
Agent, diluent.
" cation aqueous polyurethane FS20566M " (" polyurethane industrial " 2009 years as written by Yang Wentang, Yan Qiao, Tang Li etc.
Volume 24 the 5th phase) disclosed in the preparation method of the organic-silicon-modified cation aqueous polyurethane of response type, in its raw material: polymerization is single
Body includes hydroxyl alkyl-terminated polysiloxane, aminopropyl trimethoxysilane coupling agent；Modifying agent includes polybutadiene diol, different fluorine that
Ketone diisocyanate, cation chain extender N methyldiethanol amine, nonionic chain extender trimethylolpropane；Adjuvant is quaternary ammonium
Change reagent iodomethane, nertralizer acetic acid, diluent N-Methyl pyrrolidone.
The method is with the most hydrophilic polybutadiene diol for flexible polyurethane monomer the trifunctional that uses nonionic
Small molecule monomer trimethylolpropane is chain extender, causes product to be difficult to emulsifying, and emulsion particle diameter is relatively big, particle diameter wider distribution and steady
Qualitative the highest；Due to select monomer hydrophilic poor, macromolecule has the intramolecular crosslinking of higher density in addition, inevitable requirement its
There is very strong cation characteristic so that macromolecule can not spread to fiber with bigger quantity and adsorb.Additionally, this macromolecule knot
Polysiloxanes chain link in structure is shorter and content is the highest, and the soft feel style being unsuitable for textile arranges.
Summary of the invention
The technical problem to be solved is: provide the tree-shaped cladodification cationic silicone that a kind of low-density cross-links
Preparation method of microemulsion and products thereof.The tree-shaped cladodification cationic silicone microemulsion of the low-density crosslinking that the present invention provides
Product.There is cladodification polysiloxanes long-chain and the cation group of higher density, and there is the interlinkage structure of certain density simultaneously,
The high-elastic soft and smooth feel of all kinds of textile product can be obviously improved, be widely used in the high-elastic soft and smooth feel wind of all kinds of tatting textile product
Lattice arrange.
The present invention solves above-mentioned technical problem and be the technical scheme is that
The preparation method of tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking, it is characterised in that: include with
Lower step:
(1) raw material prepares: polymerization monomer, adjuvant and water；Wherein: polymerization monomer include polyisocyanates, in poly-end hydrocarbon
Based polysiloxane linear body, chain extender, silane coupler；Adjuvant includes polymerization catalyst, diluent, nertralizer；
Polyisocyanates is the mixture of diisocyanate and diisocyanate trimer；
In poly-end alkyl polysiloxanes linear body be molecular weight be the hydroxyl alkyl-terminated polydimethylsiloxane of 3000～6000
A kind of or one of α, ω-two aminopropyl that molecular weight is 3000～6000 end-blocking polydimethylsiloxane；
Chain extender be nonionic chain extender 1,4-butanediol, neopentyl glycol, molecular weight be the linear poly-second of 1000～1500
One or both and cation chain extender N methyldiethanol amine of allyl diglycol methyl ether, N butyl diethanol amine a kind of mixed
Compound；
Silane coupler be gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane,
The one of 3-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxy diethoxy silane；
The molfraction of each component is: polyisocyanates 9～10, in poly-end alkyl polysiloxanes linear body 3～5, chain extension
Agent 4～6, wherein diisocyanate molfraction is 10:(1.1～1.3 with the ratio of diisocyanate trimer molfraction),
Cation chain extender is 10:(1～2 with the ratio of nonionic chain extender molfraction), silane coupler molfraction is that (two is different
Poly-end alkyl polysiloxanes linear body molar part in cyanate molfraction+diisocyanate trimer molfraction × 1.5-
Number-nonionic chain extender molfraction-cation chain extender molfraction) × (1.2～1.6)；
(2) step of pretreatment, this step by poly-end alkyl polysiloxanes linear body carry out under vacuum, heating condition
Dehydration pretreatment；
(3) just poly-step, this step will be dehydrated pretreated in poly-end alkyl polysiloxanes linear body and part two
Isocyanates, polymerization catalyst carry out the most poly-reaction, prepare polysiloxanes just aggressiveness；
(4) step of pre-polymerization, the polysiloxanes that low-density is cross-linked by this step just aggressiveness and nonionic chain extender, two isocyanides
Acid esters trimer, residue di-isocyanate reaction, prepare the tree-shaped cladodification polysiloxane pre polymers body of low-density crosslinking；
(5) step of chain extension, the tree-shaped cladodification polysiloxane pre polymers body that low-density is cross-linked by this step and cation chain extension
Agent, portion of diluent reaction, prepare the tree-shaped cladodification cationic silicone intermediate of low-density crosslinking；
(6) step blocked, tree-shaped cladodification cationic silicone intermediate that low-density is cross-linked by this step and silane
Coupling agent reacts, and prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking；
(7) step of emulsifying, tree-shaped cladodification cationic silicone macromolecule that low-density is cross-linked by this step, neutralization
Agent, residue diluent, water mixing emulsifying, prepare the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.
By such scheme, described diisocyanate is toluene di-isocyanate(TDI) or isophorone diisocyanate；Described
Diisocyanate trimer be hexamethylene diisocyanate trimer.
By such scheme, described polymerization catalyst is stannous octoate or dibutyl tin laurate；Polymerization catalyst
Consumption is the 0.03～0.04% of polymerization total monomer weight；
Diluent is the one in acetone, butanone, methyl pyrrolidone；In chain extension step, the consumption of diluent is for making
Polyreaction is normally carried out, and in emulsion process, the consumption of diluent is for can make emulsion process be normally carried out；
Nertralizer is glacial acetic acid, and nertralizer is 0.9～1.2 times of cation chain extender weight；
Water is the soft water that total hardness is less than 50ppmCaO；Water with the solid content that total consumption is adjustable product of diluent is
30～40%.
In such scheme, the temperature of step (2) vacuum dehydration is 105～110 DEG C, vacuum be-0.100～-
0.098MPa, dewatering time is 60～90min.
In such scheme, in the first poly-reaction of step (3) addition is diisocyanate total amount the 10 of diisocyanate
～40wt%.
In such scheme, the first poly-reaction temperature of step (3) is 80～90 DEG C, and the response time is 60～90min.
In such scheme, the prepolymerization reaction temperature of step (4) is 80～90 DEG C, and the response time is 90～120min.
In such scheme, the chain extending reaction temperature of step (5) is 50～60 DEG C, and the response time is 40～60min.
In such scheme, the end capping reaction temperature of step (6) is 50～60 DEG C, and the response time is 50～80min.
In such scheme, the emulsifying in step (7) is to add remaining diluent under the conditions of system temperature less than 50 DEG C；
Add nertralizer, stirring, be then added to water, stand, deaeration.
In such scheme, the preparation method of the tree-shaped cladodification cationic silicone microemulsion of described low-density crosslinking,
Specifically include following steps:
(1) raw material is prepared；
(2) in inciting somebody to action, poly-end alkyl polysiloxanes linear body puts into reactor；Heated material is to 105～110 DEG C ,-0.100
～under the vacuum of-0.098MPa, process 60～90min；
(3) material of step (2) is cooled to 70～75 DEG C, puts into polymerization catalyst；
In 20～30min, uniformly put into 10～the diisocyanate of 40% maintain stirring, control temperature of reaction system
It it is 75～80 DEG C；
Heating up and controlling temperature of reaction system is 80～90 DEG C, insulation reaction 60～90min, prepares the poly-of low-density crosslinking
Siloxanes just aggressiveness.
(4) reaction system of step (3) is cooled to 75～80 DEG C；
Put into nonionic chain extender, diisocyanate trimer, residue diisocyanate and maintain stirring, controlling reactant
Be temperature be 75～80 DEG C, maintain stirring reaction 20～30min；
Heating up and controlling reaction temperature is 80～90 DEG C, insulation reaction 90～120min, prepares the tree-shaped of low-density crosslinking
Cladodification polysiloxane pre polymers body.
(5) reaction system of step (4) is cooled to 50～55 DEG C；
Being uniformly added into cation chain extender in 20～30min, maintaining reaction temperature is 50～60 DEG C；
Maintaining reaction temperature is 50～60 DEG C, continues stirring reaction 40～60min, and period adds the most in good time and is less than
The diluent of total amount 70%, to control the viscosity of reaction system, prepares the tree-shaped cladodification cationic silicone of low-density crosslinking
Intermediate；
(6) temperature maintaining step (5) reaction system is 50～60 DEG C；
In 10～20min, be uniformly added into silane coupler, afterwards maintain temperature be 50～60 DEG C, stirring reaction 50～
80min, prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking；
(7)
(7.1) in the reaction system of step (6), add remaining diluent, and be cooled to less than 50 DEG C；
(7.2) add nertralizer, and maintenance system temperature is 45～50 DEG C, stirs 15～20min；
(7.3) improve blender rotating speed, the reaction system in (7.2) reactor adds in 10～20min water, it
Rear maintenance stirs 30～50min；
(7.4) standing, deaeration, prepares the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.
The preparation method system of a kind of tree-shaped cladodification cationic silicone microemulsion cross-linked according to above-mentioned low-density is provided
The tree-shaped cladodification cationic silicone microemulsion product obtained.Compared with prior art, the inventive method have the following advantages and
Feature:
1, the organosilicon macromolecule that the present invention provides has the cladodification polysiloxanes long-chain of higher density, more cation
Group, more low-density long interlinkage and a small amount of polyether lateral chain, introduce the carbamic acid of higher density in its main chain simultaneously
Ester structure, material structure is novel, and feel unique style, the high-elastic soft and smooth feel style that can be used for all kinds of tatting textile product is whole
Reason.
2, the present invention use a small amount of diisocyanate with in poly-end alkyl polysiloxanes linear body carry out the most poly-, it is thus achieved that long-chain
Just aggressiveness, then use diisocyanate trimer with in the first aggressiveness of long-chain of poly-end alkyl polysiloxanes linear body react, auxiliary
In the way of a small amount of silane coupler blocks, it is thus achieved that there is the cladodification polysiloxanes long-chain of higher density and more low-density length
The organosilicon macromolecule of chain crosslinking, obtains balance in its " fluffy softness " and " high-elastic soft cunning " two kinds of contradiction feel styles, with
Time the reaction in each stage also can be made more steady, controlled, the viscosity of reaction system is relatively small.Wherein: use a small amount of two different
Cyanate with in poly-end alkyl polysiloxanes linear body carry out the most poly-technical measures, it is thus achieved that there is the polysiloxanes of longer chain joint
Macromolecule just aggressiveness, is not only advantageous to " high-elastic soft and smooth " feel style characteristic of product, and can make the reaction in each stage more
Adding steady, controlled, the viscosity of reaction system is relatively small.
3, the inventive method uses segmentation reaction and by the design on the opportunity of feeding intake, and the controllability of product structure is relatively strong, has
It is beneficial to obtain tree-shaped cladodification long-chain polysiloxane structure definitely, it is ensured that " high-elastic soft and smooth " feel style characteristic of product.
Controllability is good, and technique is smooth, it is easy to manipulation.There is good market prospect；Product does not contains emulsifying agent, and stability of emulsion is good,
Solvent is low, safety and environmental protection, easy to use；Product has good application performance, and effect is notable.
Detailed description of the invention
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of embodiment 1 low-density of the present invention crosslinking
The raw material of this preparation method includes:
1, polymerization monomer
Diisocyanate: toluene di-isocyanate(TDI) 8.0mol (1393.2g)
Diisocyanate trimer: hexamethylene diisocyanate trimer 1.0mol (504.6g)
In poly-end alkyl polysiloxanes linear body: molecular weight is the hydroxyl alkyl-terminated polydimethylsiloxane 4.0mol of 5000
(20000.0g)
Chain extender: nonionic chain extender 1,4-butanediol 0.2mol (18.0g) and molecular weight are the linear polyethylene of 1000
Ethylene glycol monomethyl ether 0.5mol (500.0g), cation chain extender N methyldiethanol amine 4.5mol (536.2g)
Silane coupler: gamma-aminopropyl-triethoxy-silane 0.4mol (88.5g)
2, adjuvant
Polymerization catalyst: dibutyl tin laurate (7.0g)
Diluent: acetone (7000.0g)
Nertralizer: glacial acetic acid (550.0g)
3, water: the total hardness soft water (35253.0g) less than 50ppmCaO
The concrete steps of this preparation method:
(1) step of pretreatment, this step by poly-end alkyl polysiloxanes linear body carry out under vacuum, heating condition
Dehydration pretreatment；Particularly as follows:
(1.1) in inciting somebody to action, poly-end alkyl polysiloxanes linear body puts into reactor；
(1.2) heated material is to 105～110 DEG C, processes 80min under the vacuum of-0.099MPa.
(2) just poly-step, this step will be dehydrated pretreated in poly-end alkyl polysiloxanes linear body and part two
Isocyanates, polymerization catalyst carry out the most poly-reaction, prepare the tree-shaped cladodification cationic silicone just aggressiveness of low-density crosslinking；
Particularly as follows:
(2.1) material of step (1.2) is cooled to 70～75 DEG C, puts into polymerization catalyst；
(2.2) uniformly putting into the diisocyanate of 10% in 20min and maintain stirring, controlling temperature of reaction system is 75
～80 DEG C；
(2.3) heating up and control temperature of reaction system is 80～85 DEG C, insulation reaction 80min, prepares low-density crosslinking
Tree-shaped cladodification cationic silicone just aggressiveness.
(3) step of pre-polymerization, the tree-shaped cladodification cationic silicone that low-density is cross-linked by this step just aggressiveness with non-from
Sub-chain extender, diisocyanate trimer, residue di-isocyanate reaction, the tree-shaped cladodification cation preparing low-density crosslinking is gathered
Siloxanes performed polymer；Particularly as follows:
(3.1) reaction system of step (2.3) is cooled to 75～80 DEG C；
(3.2) put into nonionic chain extender, diisocyanate trimer, residue diisocyanate and maintain stirring, controlling
Temperature of reaction system is 75～80 DEG C, maintains stirring reaction 20min；
(3.3) heating up and control reaction temperature is 80～85 DEG C, insulation reaction 120min, prepares the tree-shaped of low-density crosslinking
Cladodification cationic silicone performed polymer.
(4) step of chain extension, change tree-shaped cladodification cationic silicone performed polymer that low-density cross-links by step and sun from
Sub-chain extender, portion of diluent react, and prepare the tree-shaped cladodification cationic silicone intermediate of low-density crosslinking；Particularly as follows:
(4.1) reaction system of step (3.3) is cooled to 50～55 DEG C；
(4.2) being uniformly added into cation chain extender in 30min, maintaining reaction temperature is 50～55 DEG C；
(4.3) maintaining reaction temperature is 50～55 DEG C, continues stirring reaction 50min, and period adds the most in good time and do not surpasses
Cross the diluent of total amount 70%, to control the viscosity of reaction system, prepare the tree-shaped poly-silica of cladodification cation of low-density crosslinking
Alkane intermediate.
(5) step blocked, tree-shaped cladodification cationic silicone intermediate that low-density is cross-linked by this step and silane
Coupling agent reacts, and prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking；Particularly as follows:
(5.1) temperature maintaining step (4.3) reaction system is 50～55 DEG C；
(5.2) being uniformly added into silane coupler in 10min, maintaining temperature afterwards is 55～60 DEG C, stirring reaction
60min, prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking.
(6) step of emulsifying, tree-shaped cladodification cationic silicone macromolecule that low-density is cross-linked by this step, neutralization
Agent, residue diluent, water mixing emulsifying, prepare the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.Specifically
For:
(6.1) in the reaction system of step (5.2), add remaining diluent, and be cooled to less than 50 DEG C；
(6.2) add nertralizer, and maintenance system temperature is 45～50 DEG C, stirs 20min；
(6.3) improve blender rotating speed, the reaction system in (6.2) reactor adds in 15min water, ties up afterwards
Hold stirring 50min；
(6.4) standing, deaeration, prepares the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.
Product purpose usage prepared by the inventive method: whole for the high-elastic soft and smooth feel style of all kinds of tatting textile products
Reason；Use with tradition amino-modified silicone softening agent or organic silicon modified by polyether softening agent blending, all kinds of shuttle can be obviously improved
Knit the high-elastic soft and smooth feel of textile product.There is good market prospect, product safety environmental protection, easy to use.
Product prepared by the inventive method stores: finished product must seal in shady and cool, the place of being dried and preserve.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of embodiment 2 low-density of the present invention crosslinking
The raw material of this preparation method includes:
1, polymerization monomer
Diisocyanate: isoflurane chalcone diisocyanate 9.0mol (2000.6g)
Diisocyanate trimer: hexamethylene diisocyanate trimer 1.0mol (504.6g)
In poly-end alkyl polysiloxanes linear body: molecular weight is the hydroxyl alkyl-terminated polydimethylsiloxane 4.8mol of 3000
(14400.0g)
Chain extender: nonionic chain extender be molecular weight be linear polyethylene ethylene glycol monomethyl ether 0.9mol of 1000
(900.0g), cation chain extender N butyl diethanol amine 4.5mol (725.6g)
Silane coupler: γ-aminopropyltriethoxy diethoxy silane 0.45mol (86.1g)
2, adjuvant
Polymerization catalyst: stannous octoate (5.7g)
Diluent: butanone (4800.0g)
Nertralizer: glacial acetic acid (750.0g)
3, water: the total hardness soft water (26159.0g) less than 50ppmCaO
The concrete steps of this preparation method:
(1) step of pretreatment, this step by poly-end alkyl polysiloxanes linear body carry out under vacuum, heating condition
Dehydration pretreatment；Particularly as follows:
(1.1) in inciting somebody to action, poly-end alkyl polysiloxanes linear body puts into reactor；
(1.2) heated material is to 100～105 DEG C, processes 90min under the vacuum of-0.098MPa.
(2) just poly-step, this step will be dehydrated pretreated in poly-end alkyl polysiloxanes linear body and part two
Isocyanates, polymerization catalyst carry out the most poly-reaction, prepare the tree-shaped cladodification cationic silicone just aggressiveness of low-density crosslinking；
Particularly as follows:
(2.1) material of step (1.2) is cooled to 70～75 DEG C, puts into polymerization catalyst；
(2.2) uniformly putting into the diisocyanate of 30% in 25min and maintain stirring, controlling temperature of reaction system is 75
～80 DEG C；
(2.3) heating up and control temperature of reaction system is 85～90 DEG C, insulation reaction 90min, prepares low-density crosslinking
Tree-shaped cladodification cationic silicone just aggressiveness.
(3) step of pre-polymerization, the tree-shaped cladodification cationic silicone that low-density is cross-linked by this step just aggressiveness with non-from
Sub-chain extender, diisocyanate trimer, residue di-isocyanate reaction, the tree-shaped cladodification cation preparing low-density crosslinking is gathered
Siloxanes performed polymer；Particularly as follows:
(3.1) reaction system of step (2.3) is cooled to 75～80 DEG C；
(3.2) put into nonionic chain extender, diisocyanate trimer, residue diisocyanate and maintain stirring, controlling
Temperature of reaction system is 75～80 DEG C, maintains stirring reaction 30min；
(3.3) heating up and control reaction temperature is 85～90 DEG C, insulation reaction 100min, prepares the tree-shaped of low-density crosslinking
Cladodification cationic silicone performed polymer.
(4) step of chain extension, change tree-shaped cladodification cationic silicone performed polymer that low-density cross-links by step and sun from
Sub-chain extender, portion of diluent react, and prepare the tree-shaped cladodification cationic silicone intermediate of low-density crosslinking；Particularly as follows:
(4.1) reaction system of step (3.3) is cooled to 50～55 DEG C；
(4.2) being uniformly added into cation chain extender in 20min, maintaining reaction temperature is 55～60 DEG C；
(4.3) maintaining reaction temperature is 55～60 DEG C, continues stirring reaction 50min, and period adds the most in good time and do not surpasses
Cross the diluent of total amount 70%, to control the viscosity of reaction system, prepare the tree-shaped poly-silica of cladodification cation of low-density crosslinking
Alkane intermediate.
(5) step blocked, tree-shaped cladodification cationic silicone intermediate that low-density is cross-linked by this step and silane
Coupling agent reacts, and prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking；Particularly as follows:
(5.1) temperature maintaining step (4.3) reaction system is 55～60 DEG C；
(5.2) being uniformly added into silane coupler in 20min, maintaining temperature afterwards is 55～60 DEG C, stirring reaction
70min, prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking.
(6) step of emulsifying, tree-shaped cladodification cationic silicone macromolecule that low-density is cross-linked by this step, neutralization
Agent, residue diluent, water mixing emulsifying, prepare the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.Specifically
For:
(6.1) in the reaction system of step (5.2), add remaining diluent, and be cooled to less than 50 DEG C；
(6.2) add nertralizer, and maintenance system temperature is 45～50 DEG C, stirs 20min；
(6.3) improve blender rotating speed, the reaction system in (6.2) reactor adds in 15min water, ties up afterwards
Hold stirring 30min；
(6.4) standing, deaeration, prepares the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.
Product purpose usage prepared by the inventive method: whole for the high-elastic soft and smooth feel style of all kinds of tatting textile products
Reason；Use with tradition amino-modified silicone softening agent or organic silicon modified by polyether softening agent blending, all kinds of shuttle can be obviously improved
Knit the high-elastic soft and smooth feel of textile product.There is good market prospect, product safety environmental protection, easy to use.
Product prepared by the inventive method stores: finished product must seal in shady and cool, the place of being dried and preserve.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of embodiment 3 low-density of the present invention crosslinking
The raw material of this preparation method includes:
1, polymerization monomer
Diisocyanate: isoflurane chalcone diisocyanate 8.5mol (1889.5g)
Diisocyanate trimer: hexamethylene diisocyanate trimer 1.1mol (555.0g)
In poly-end alkyl polysiloxanes linear body: molecular weight is the α of 4000, ω-two aminopropyl end-blocking polydimethylsiloxanes
Alkane 3.6mol (14400.0g)
Chain extender: nonionic chain extender be molecular weight be linear polyethylene ethylene glycol monomethyl ether 0.8mol of 1300
(1040.0g), cation chain extender N methyldiethanol amine 5.0mol (595.8g)
Silane coupler: γ-aminopropyltriethoxy diethoxy silane 1.0mol (191.3g)
2, adjuvant
Polymerization catalyst: stannous octoate (6.9g)
Diluent: methyl pyrrolidone (4400.0g)
Nertralizer: glacial acetic acid (660.0g)
3, water: the total hardness soft water (24155.0g) less than 50ppmCaO
The concrete steps of this preparation method:
(1) step of pretreatment, this step by poly-end alkyl polysiloxanes linear body carry out under vacuum, heating condition
Dehydration pretreatment；Particularly as follows:
(1.1) in inciting somebody to action, poly-end alkyl polysiloxanes linear body puts into reactor；
(1.2) heated material is to 105～110 DEG C, processes 80min under the vacuum of-0.098MPa.
(2) just poly-step, this step will be dehydrated pretreated in poly-end alkyl polysiloxanes linear body and part two
Isocyanates, polymerization catalyst carry out the most poly-reaction, prepare the tree-shaped cladodification cationic silicone just aggressiveness of low-density crosslinking；
Particularly as follows:
(2.1) material of step (1.2) is cooled to 70～75 DEG C, puts into polymerization catalyst；
(2.2) uniformly putting into the diisocyanate of 20% in 20min and maintain stirring, controlling temperature of reaction system is 75
～80 DEG C；
(2.3) heating up and control temperature of reaction system is 85～90 DEG C, insulation reaction 90min, prepares low-density crosslinking
Tree-shaped cladodification cationic silicone just aggressiveness.
(3) step of pre-polymerization, the tree-shaped cladodification cationic silicone that low-density is cross-linked by this step just aggressiveness with non-from
Sub-chain extender, diisocyanate trimer, residue di-isocyanate reaction, the tree-shaped cladodification cation preparing low-density crosslinking is gathered
Siloxanes performed polymer；Particularly as follows:
(3.1) reaction system of step (2.3) is cooled to 75～80 DEG C；
(3.2) put into nonionic chain extender, diisocyanate trimer, residue diisocyanate and maintain stirring, controlling
Temperature of reaction system is 75～80 DEG C, maintains stirring reaction 20min；
(3.3) heating up and control reaction temperature is 85～90 DEG C, insulation reaction 120min, prepares the tree-shaped of low-density crosslinking
Cladodification cationic silicone performed polymer.
(4) step of chain extension, change tree-shaped cladodification cationic silicone performed polymer that low-density cross-links by step and sun from
Sub-chain extender, portion of diluent react, and prepare the tree-shaped cladodification cationic silicone intermediate of low-density crosslinking；Particularly as follows:
(4.1) reaction system of step (3.3) is cooled to 50～55 DEG C；
(4.2) being uniformly added into cation chain extender in 30min, maintaining reaction temperature is 50～55 DEG C；
(4.3) maintaining reaction temperature is 50～55 DEG C, continues stirring reaction 40min, and period adds the most in good time and do not surpasses
Cross the diluent of total amount 70%, to control the viscosity of reaction system, prepare the tree-shaped poly-silica of cladodification cation of low-density crosslinking
Alkane intermediate.
(5) step blocked, tree-shaped cladodification cationic silicone intermediate that low-density is cross-linked by this step and silane
Coupling agent reacts, and prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking；Particularly as follows:
(5.1) temperature maintaining step (4.3) reaction system is 50～55 DEG C；
(5.2) being uniformly added into silane coupler in 20min, maintaining temperature afterwards is 55～60 DEG C, stirring reaction
60min, prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking.
(6) step of emulsifying, tree-shaped cladodification cationic silicone macromolecule that low-density is cross-linked by this step, neutralization
Agent, residue diluent, water mixing emulsifying, prepare the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.Specifically
For:
(6.1) in the reaction system of step (5.2), add remaining diluent, and be cooled to less than 50 DEG C；
(6.2) add nertralizer, and maintenance system temperature is 45～50 DEG C, stirs 20min；
(6.3) improve blender rotating speed, the reaction system in (6.2) reactor adds in 15min water, ties up afterwards
Hold stirring 50min；
(6.4) standing, deaeration, prepares the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.
Product purpose usage prepared by the inventive method: whole for the high-elastic soft and smooth feel style of all kinds of tatting textile products
Reason；Use with tradition amino-modified silicone softening agent or organic silicon modified by polyether softening agent blending, all kinds of shuttle can be obviously improved
Knit the high-elastic soft and smooth feel of textile product.There is good market prospect, product safety environmental protection, easy to use.
Product prepared by the inventive method stores: finished product must seal in shady and cool, the place of being dried and preserve.
The foregoing is only each concrete raw material cited by the preferred embodiments of the present invention, the actually present invention, and each former
The bound of material, interval value, and the bound of technological parameter (such as temperature, time etc.), interval value can realize this
Bright, embodiment numerous to list herein.
Therefore, above example is not in order to limit the present invention, and those skilled in the art is at technical solution of the present invention model
The usual variations and alternatives carried out in enclosing all should comprise within the scope of the present invention.
Claims (10)
1. the preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking, it is characterised in that: include following
Step:
(1) raw material prepares: polymerization monomer, adjuvant and water；Wherein: polymerization monomer include polyisocyanates, in poly-end alkyl gather
Siloxanes linear body, chain extender, silane coupler；Adjuvant includes polymerization catalyst, diluent, nertralizer；
Polyisocyanates is the mixture of diisocyanate and diisocyanate trimer；
In poly-end alkyl polysiloxanes linear body be molecular weight be the one of the hydroxyl alkyl-terminated polydimethylsiloxane of 3000～6000
Kind or α, ω-two aminopropyl that molecular weight is 3000～6000 block the one of polydimethylsiloxane；
Chain extender be nonionic chain extender 1,4-butanediol, neopentyl glycol, molecular weight be the linear polyethylene second of 1000～1500
One or both and cation chain extender N methyldiethanol amine, a kind of mixing of N butyl diethanol amine of glycol methyl ether
Thing；
Silane coupler is gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, 3-mercapto
The one of propyl-triethoxysilicane, γ-aminopropyltriethoxy diethoxy silane；
The molfraction of each component is: polyisocyanates 9～10, in poly-end alkyl polysiloxanes linear body 3～5, chain extender 4～
6, wherein the ratio of diisocyanate molfraction and diisocyanate trimer molfraction is 10:(1.1～1.3), sun from
Sub-chain extender is 10:(1～2 with the ratio of nonionic chain extender molfraction), silane coupler molfraction is (two Carbimide .s
Poly-end alkyl polysiloxanes linear body molfraction in ester molfraction+diisocyanate trimer molfraction × 1.5--non-
Ion chain extender molfraction-cation chain extender molfraction) × (1.2～1.6)；
(2) step of pretreatment, this step by poly-end alkyl polysiloxanes linear body be dehydrated under vacuum, heating condition
Pretreatment；
(3) just poly-step, this step will be dehydrated pretreated in poly-end alkyl polysiloxanes linear body and part two isocyanide
Acid esters, polymerization catalyst carry out the most poly-reaction, prepare polysiloxanes just aggressiveness；
(4) step of pre-polymerization, the polysiloxanes that low-density is cross-linked by this step just aggressiveness and nonionic chain extender, diisocyanate
Trimer, residue di-isocyanate reaction, prepare the tree-shaped cladodification polysiloxane pre polymers body of low-density crosslinking；
(5) step of chain extension, the tree-shaped cladodification polysiloxane pre polymers body that low-density is cross-linked by this step and cation chain extender, portion
Divide diluent reaction, prepare the tree-shaped cladodification cationic silicone intermediate of low-density crosslinking；
(6) step blocked, the tree-shaped cladodification cationic silicone intermediate that low-density is cross-linked by this step is with silane coupled
Agent is reacted, and prepares the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking；
(7) step of emulsifying, tree-shaped cladodification cationic silicone macromolecule that low-density is cross-linked by this step, nertralizer, surplus
Remaining diluent, water mixing emulsifying, prepare the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: described diisocyanate is toluene di-isocyanate(TDI) or isophorone diisocyanate；Two described isocyanides
Acid esters trimer is hexamethylene diisocyanate trimer.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: described polymerization catalyst is stannous octoate or dibutyl tin laurate；The consumption of polymerization catalyst is poly-
Close the 0.03～0.04% of total monomer weight；
Diluent is the one in acetone, butanone, methyl pyrrolidone；In chain extension step, the consumption of diluent is for can make polymerization
Reaction is normally carried out, and in emulsion process, the consumption of diluent is for can make emulsion process be normally carried out；
Nertralizer is glacial acetic acid, and nertralizer is 0.9～1.2 times of cation chain extender weight；
Water is the soft water that total hardness is less than 50ppmCaO；The solid content that total consumption is adjustable product of water and diluent be 30～
40%；
The temperature of step (2) vacuum dehydration is 105～110 DEG C, and vacuum is-0.100～-0.098MPa, and dewatering time is 60
～90min；
Emulsifying in step (7) is to add remaining diluent under the conditions of system temperature less than 50 DEG C；Add nertralizer, stir
Mix, be then added to water, stand, deaeration.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: in the first poly-reaction of step (3) addition is diisocyanate total amount the 10～40wt% of diisocyanate.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: the first poly-reaction temperature of step (3) is 80～90 DEG C, the response time is 60～90min.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: the prepolymerization reaction temperature of step (4) is 80～90 DEG C, the response time is 90～120min.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: the chain extending reaction temperature of step (5) is 50～60 DEG C, the response time is 40～60min.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: the end capping reaction temperature of step (6) is 50～60 DEG C, the response time is 50～80min.
The preparation method of the tree-shaped cladodification cationic silicone microemulsion of low-density the most according to claim 1 crosslinking,
It is characterized in that: specifically include following steps:
(1) raw material is prepared；
(2) in inciting somebody to action, poly-end alkyl polysiloxanes linear body puts into reactor；Heated material to 105～110 DEG C ,-0.100～-
60～90min are processed under the vacuum of 0.098MPa；
(3) material of step (2) is cooled to 70～75 DEG C, puts into polymerization catalyst；
Uniformly putting into 10～the diisocyanate of 40% maintain stirring in 20～30min, controlling temperature of reaction system is 75
～80 DEG C；
Heating up and controlling temperature of reaction system is 80～90 DEG C, insulation reaction 60～90min, prepares the poly-silica of low-density crosslinking
Alkane just aggressiveness.
(4) reaction system of step (3) is cooled to 75～80 DEG C；
Put into nonionic chain extender, diisocyanate trimer, residue diisocyanate and maintain stirring, controlling reaction system temperature
Degree is 75～80 DEG C, maintains stirring reaction 20～30min；
Heating up and controlling reaction temperature is 80～90 DEG C, insulation reaction 90～120min, prepares the tree-shaped cladodification of low-density crosslinking
Polysiloxane pre polymers body.
(5) reaction system of step (4) is cooled to 50～55 DEG C；
Being uniformly added into cation chain extender in 20～30min, maintaining reaction temperature is 50～60 DEG C；
Maintaining reaction temperature is 50～60 DEG C, continues stirring reaction 40～60min, and period adds less than total amount the most in good time
The diluent of 70%, to control the viscosity of reaction system, prepares in the middle of the tree-shaped cladodification cationic silicone of low-density crosslinking
Body；
(6) temperature maintaining step (5) reaction system is 50～60 DEG C；
Being uniformly added into silane coupler in 10～20min, maintaining temperature afterwards is 50～60 DEG C, stirring reaction 50～80min,
Prepare the tree-shaped cladodification cationic silicone macromolecule of low-density crosslinking；
(7) (7.1) add remaining diluent in the reaction system of step (6), and are cooled to less than 50 DEG C；
(7.2) add nertralizer, and maintenance system temperature is 45～50 DEG C, stirs 15～20min；
(7.3) improve blender rotating speed, the reaction system in (7.2) reactor adds in 10～20min water, ties up afterwards
Hold stirring 30～50min；
(7.4) standing, deaeration, prepares the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking.
10. according to the preparation of the tree-shaped cladodification cationic silicone microemulsion of low-density crosslinking any one of claim 1-9
The tree-shaped cladodification cationic silicone microemulsion product that method prepares.
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