CN103254414A - Sulfonic acid type polyester polyol and sulfonic acid type waterborne polyurethane as well as preparation methods thereof - Google Patents
Sulfonic acid type polyester polyol and sulfonic acid type waterborne polyurethane as well as preparation methods thereof Download PDFInfo
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- CN103254414A CN103254414A CN2013101577632A CN201310157763A CN103254414A CN 103254414 A CN103254414 A CN 103254414A CN 2013101577632 A CN2013101577632 A CN 2013101577632A CN 201310157763 A CN201310157763 A CN 201310157763A CN 103254414 A CN103254414 A CN 103254414A
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- sulfonic acid
- acid type
- polyester polyol
- type polyester
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 76
- 239000004814 polyurethane Substances 0.000 title claims abstract description 51
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 51
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000010792 warming Methods 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- -1 amyl alcohol ester Chemical class 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 150000007520 diprotic acids Chemical class 0.000 claims description 8
- 150000002334 glycols Chemical class 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 150000003384 small molecules Chemical class 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 5
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 claims description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 claims description 4
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical group CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical group O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241001062009 Indigofera Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical class CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses sulfonic acid type polyester polyol and sulfonic acid type waterborne polyurethane as well as preparation methods thereof. The raw material formula of the sulfonic acid type polyester polyol comprises the following components in parts by weight: 28-52 parts of isophthalic acid-5-sodium sulfonate, 110-180 parts of dihydric alcohol, 40-80 parts of a solvent, 110-190 parts of binary acid, 0.05-0.15 part of a catalyst and 0.01-0.05 part of an antioxidant. The sulfonic acid type polyester polyol is used as a raw material to prepare the sulfonic acid type waterborne polyurethane with high solid content. When the resin (sulfonic acid type waterborne polyurethane) is used in the industries of construction, woodware coatings and textiles, paper adhesives and the like, the drying speed is increased, the number of times for manual coating is reduced, and the transportation cost is reduced at the same time, so that the sulfonic acid type waterborne polyurethane is an energy-saving and environment-friendly product.
Description
Technical field
The present invention relates to chemistry painting industry and adhesive area, relate in particular to a kind of sulfonic acid type polyester polyol, sulfonic acid type aqueous polyurethane and preparation method thereof.
Background technology
Aqueous polyurethane is an important component part in the material industry because it has good weather resisteant, wear resistance, lower temperature resistance, volatile organic compounds (VOC) content is low and advantage such as organic solvent-free can be widely used in fields such as coating and sizing agent.Solid content is an important indicator weighing aqueous polyurethane, and the height of solid content all has material impact to indexs such as production efficiency, transportation cost, use propertieies.The solid content of traditional water based polyurethane has only about 35%, and the cost height needs to consume lot of energy and time drying.Need the aqueous polyurethane emulsion of high solids content in many Application Areass, the aqueous polyurethane of high-solid level can improve plant factor, reduces transportation and storage cost, reduces construction times, improves the advantages such as fullness ratio of paint film.
Polyester polyol is the important source material of synthetic water based polyurethane, and utilizing the waterborne polyester polyvalent alcohol to prepare aqueous polyurethane is the new direction of studying both at home and abroad.At present, aqueous polyurethane mainly is to utilize the hydroxyl telechelic polyester polyvalent alcohol to introduce self-emulsifying functional group, in amine and after in water, be separated into the carboxylic acid type aqueous polyurethane.But because traditional carboxylic acid type aqueous polyurethane is slightly acidic, hydrophilic ability is relatively poor, therefore is difficult to make high solids content, high-performance water-based polyurethane.And the amine neutralizing agent has very strong toxic side effect, is unfavorable for environmental protection and staff's health.And the sulfonic acid type aqueous polyurethane belongs to strong acid and strong base salt, and its hydrophilic ability is strong, is applicable to the aqueous polyurethane of preparation high solids content.The sulfonate type aqueous polyurethane need not the amine neutralization in preparation process in addition, need not organic solvent diluting in the construction, compliance with environmental protection requirements.At present a lot of R﹠D institutions and producer utilize thionamic acid sodium (A95) also consolidating of aqueous polyurethane can be contained and accomplish more than 50%, but, adopt A95 in the process of synthetic water based polyurethane, will add the dispersion that a large amount of organic solvents just is conducive to prepolymer, requirement to dispersing apparatus is relatively stricter, and batch stability is also poor.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of sulfonic acid type polyester polyol, sulfonic acid type aqueous polyurethane and preparation method thereof, utilize homemade sulfonic acid type polyester polyol for feedstock production high solid aquosity urethane, be intended to solve existing problem in existing carboxylic acid type aqueous polyurethane and the A95 type aqueous polyurethane preparation process.
Technical scheme of the present invention is as follows:
A kind of sulfonic acid type polyester polyol, wherein, its molecular structural formula is as follows:
Wherein, m, n are positive integer, R
1=(CH
2) x, R
2=
,
,
Or (CH
2) y, x=2,3,4,5 or 6, y=3,4 or 5.
Described sulfonic acid type polyester polyol, wherein according to the parts by weight meter, its composition of raw materials consists of:
5-sodium sulfo isophthalate 28～52,110～180 parts of dibasic alcohol, 40～80 parts of solvents, 100～190 parts of diprotic acid, 0.05～0.15 part of catalyzer, 0.01～0.05 part in oxidation inhibitor.
Described sulfonic acid type polyester polyol, wherein, described dibasic alcohol is ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol or their mixture; Described diprotic acid is Succinic Acid, pentanedioic acid, hexanodioic acid, phthalic acid, m-phthalic acid, terephthalic acid, phthalic anhydride or their mixture; Described catalyzer is Mono-n-butyltin, Dibutyltin oxide, dibutyl tin dilaurate, dibutyl tin acetate, titanium isopropylate or tetrabutyl titanate; Described solvent is diethylene glycol monobutyl ether, ethylene glycol monobutyl ether or dimethylbenzene; Described oxidation inhibitor is Hypophosporous Acid, 50, triphenylphosphate or four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester.
A kind of sulfonic acid type aqueous polyurethane, wherein, described sulfonic acid type aqueous polyurethane composition of raw materials is formed and is comprised aforesaid sulfonic acid type polyester polyol; The molecular structural formula of described sulfonic acid type aqueous polyurethane is as follows:
Described sulfonic acid type aqueous polyurethane, wherein, according to the parts by weight meter, its composition of raw materials consists of:
5～10 parts of sulfonic acid type polyester polyols, 40～60 parts of polyether Glycols, 2～4 parts of small molecules dibasic alcohol, 20～40 parts of polyisocyanates, 0.05～0.15 part of catalyzer.
Described sulfonic acid type aqueous polyurethane, wherein, described polyether Glycols is polypropylene glycol ether or PTMG; Described small molecules dibasic alcohol is ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol ester, TriMethylolPropane(TMP) or their mixture; Described polyisocyanates is TDI, HDI, IPDI or their mixture; Described catalyzer is tertiary amine catalyst or organic tin catalyzer.
A kind of preparation method of aforesaid sulfonic acid type polyester polyol wherein, may further comprise the steps:
Under protection of inert gas, 28～52 parts of 5-sodium sulfo isophthalates, 110～180 parts of dibasic alcohol and solvent are warming up to 150～170 ℃ of reactions 1～2 hour for 40～80 parts, be warming up to 190～210 ℃ by 0.2 ℃/minute then, be incubated 4～8 hours, after acid number is down to 5～10mgKOH/g, be cooled to 80～120 ℃; Add 100～190 parts of diprotic acid and slowly be warming up to 140～160 ℃ of insulations 1～2 hour, add 0.05～0.15 part of catalyzer, add 3～6 parts of dibasic alcohol; Slowly be warming up to 220～230 ℃ of reactions 3～4 hours, acid number adds 0.01～0.05 part in oxidation inhibitor after being down to 10～30mgKOH/g, vacuumizes, and is incubated 6～8 hours, and acid number drops to 0.5～5mgKOH/g, stopped reaction; Be cooled to 120～140 ℃.
A kind of preparation method of aforesaid sulfonic acid type polyester polyol wherein, may further comprise the steps:
Under protection of inert gas, at 80～85 ℃ of reaction 5～8h, cooling adds water dispersion with 0.05～0.15 part of 5～10 parts of sulfonic acid type polyester polyols, 40～60 parts of polyether Glycols, 2～4 parts of small molecules dibasic alcohol, 20～40 parts of polyisocyanates and catalyzer.
Beneficial effect: a kind of sulfonic acid type aqueous polyurethane provided by the invention, adopt sulfonic acid type polyester polyol provided by the present invention to prepare the sulfonic acid type aqueous polyurethane, the reaction in the process of preparation aqueous polyurethane of sulfonic acid type polyester polyol is comparatively steady, solvent load is few, have dispersed and batch stability preferably, have good application prospects.Utilize described sulfonic acid type polyester polyol for feedstock production the high sulfonic acid type aqueous polyurethane that contains admittedly, this resin can be used for industries such as building, woodwork coating and weaving, paper tackiness agent, improve rate of drying, reduced artificial application number of times, having saved transportation cost simultaneously, is a kind of energy saving and environment friendly product.
Embodiment
The invention provides a kind of sulfonic acid type polyester polyol, sulfonic acid type aqueous polyurethane and preparation method thereof, clearer, clear and definite for making purpose of the present invention, technical scheme and effect, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
A kind of sulfonic acid type aqueous polyurethane provided by the invention, adopt the sulfonic acid type polyester polyol to prepare aqueous polyurethane, the reaction in the process of preparation aqueous polyurethane of sulfonic acid type polyester polyol is comparatively steady, solvent load is few, have dispersed and batch stability preferably, have good application prospects.
Particularly, the preparation method of described sulfonic acid type polyester polyol, synthetic route is shown below:
；
Wherein, m, n are positive integer, R
1=(CH
2) x, R
2=
,
,
Or (CH
2) y, x=2,3,4,5 or 6, y=3,4 or 5.
The preparation method's of described sulfonic acid type polyester polyol preparation process is as follows:
Under protection of inert gas, 28～52 parts of 5-sodium sulfo isophthalates, 110～180 parts of dibasic alcohol and solvent are warming up to 150～170 ℃ of reactions 1～2 hour for 40～80 parts, be warming up to 190～210 ℃ by 0.2 ℃/minute then, be incubated 4～8 hours, after acid number is down to 5～10mgKOH/g, be cooled to 80～120 ℃; Add 100～190 parts of diprotic acid and slowly be warming up to 140～160 ℃ of insulations 1～2 hour, add 0.05～0.15 part of catalyzer, add 3～6 parts of dibasic alcohol; Slowly be warming up to 220～230 ℃ of reactions 3～4 hours, acid number adds 0.01～0.05 part in oxidation inhibitor after being down to 10～30mgKOH/g, vacuumizes, and vacuum tightness rises to-0.085 gradually～-0.1Mpa, be incubated 6～8 hours, acid number drops to 0.5～5mgKOH/g, stopped reaction; Be cooled to 120～140 ℃, go out still, packing gets the sulfonic acid type polyester polyol.
Wherein, described dibasic alcohol is ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol or their mixture; Described diprotic acid is Succinic Acid, pentanedioic acid, hexanodioic acid, phthalic acid, m-phthalic acid, terephthalic acid, phthalic anhydride or their mixture.Described catalyzer is Mono-n-butyltin, Dibutyltin oxide, dibutyl tin dilaurate, dibutyl tin acetate, titanium isopropylate or tetrabutyl titanate.Described solvent is diethylene glycol monobutyl ether, ethylene glycol monobutyl ether or dimethylbenzene.Described oxidation inhibitor is Hypophosporous Acid, 50, triphenylphosphate or four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester.
Particularly, described sulfonic acid type Synthesis of Waterborne Polyurethane method, synthetic route is shown below:
Wherein, R
3=(CH
2) x, x=2,4 or 6; R
4=
,
,
Or (CH
2)
6
For the preparation of the sulfonic acid type aqueous polyurethane, its preparation process is as follows with described sulfonic acid type polyester polyol:
Under protection of inert gas; with 0.05～0.15 part of 5～10 parts of sulfonic acid type polyester polyols, 40～70 parts of polyether Glycols, 2～4 parts of small molecules dibasic alcohol, 20～40 parts of polyisocyanates and catalyzer at 80～85 ℃ of reaction 5～8h; be cooled to 30～50 ℃ and add water dispersion, obtain the high sulfonic acid type aqueous polyurethane that contains admittedly.
Described polyether Glycols is polypropylene glycol ether or PTMG.Described small molecules dibasic alcohol is ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol ester, TriMethylolPropane(TMP) or their mixture.Described polyisocyanates is TDI, HDI, IPDI or their mixture.Described catalyzer is tertiary amine catalyst or organic tin catalyzer.
The present invention utilize homemade sulfonic acid type polyester polyol for feedstock production the high sulfonic acid type aqueous polyurethane that contains admittedly, it has following advantage: 1, VOC content is few, and smell is little, environmentally safe; 2, solid content height, energy-conserving and environment-protective.This resin can be used for industries such as building, woodwork coating and weaving, paper tackiness agent, has improved rate of drying, has reduced artificial application number of times, has saved transportation cost simultaneously, is a kind of energy saving and environment friendly product.
The present invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited thereto.
Embodiment 1
(1) preparation of sulfonic acid type polyester polyol
Under nitrogen protection, with 28 parts of 5-sodium sulfo isophthalates, 110 part 1,4-butyleneglycol, 40 parts of diethylene glycol monobutyl ethers add and are equipped with in the straight four-hole bottle of agitator arm, temperature sensor, nitrogen and water-and-oil separator, are warming up to 150 ℃ of reactions 1 hour; Be warming up to 190 ℃ by 0.5 ℃/minute, be incubated 6 hours, after acid number is down to 10mgKOH/g, be cooled to 80 ℃; Add 120 parts of pentanedioic acids, slowly be warming up to 140 ℃ of insulations 2 hours, add 4 part 1,4-butyleneglycol, 0.05 part of dibutyl tin dilaurate; Slowly be warming up to 220 ℃ of reactions 3 hours, acid number is down to 0.03 part of the triphenyl phosphate ester of phosphorating behind the 30mgKOH/g, vacuumizes, and vacuum tightness rises to-0.095Mpa gradually, is incubated 6 hours, and acid number drops to 5mgKOH/g, stopped reaction; Be cooled to 120 ℃, go out still, make the sulfonic acid type polyester polyol.Its performance perameter is as follows:
| Outward appearance | Acid number (mgKOH/g) | Hydroxyl value (mgKOH/g) | Water ratio (%) |
| The transparent glue of little Huang | 5 | 57 | 0.02 |
(2) height contains the sulfonic acid type Synthesis of Waterborne Polyurethane admittedly
Under nitrogen protection; with 60 parts of 10 parts of sulfonic acid type polyester polyols, the PTMG (molecular weight 2000) of step (1), 1; 0.05 part of 3 parts of 4-butyleneglycols, 32 parts of IPDI and dibutyl tin dilaurate are at 80 ℃ of reaction 8h; be cooled to 40 ℃ and add water dispersion, obtain aqueous polyurethane dispersion.Its performance perameter is as follows:
| Outward appearance | Admittedly contain (%) | Particle diameter | Viscosity (cps) |
| The little indigo plant of white | 55 | 118 | 1200 |
Embodiment 2
(1) preparation of sulfonic acid type polyester polyol
Under nitrogen protection, with 52 parts of 5-sodium sulfo isophthalates, 180 part 1,5-pentanediol, 80 parts of ethylene glycol monobutyl ethers add and are equipped with in the straight four-hole bottle of agitator arm, temperature sensor, nitrogen and water-and-oil separator, are warming up to 160 ℃ of reactions 1.5 hours; Be warming up to 200 ℃ by 0.2 ℃/minute, be incubated 6 hours, after acid number is down to 6mgKOH/g, be cooled to 100 ℃; Add 190 parts of hexanodioic acids, slowly be warming up to 155 ℃ of insulations 1.5 hours, add 6 part 1,5-pentanediol, 0.1 part of dibutyl tin acetate; Slowly be warming up to 220 ℃ of reactions 3 hours, acid number adds 0.02 part of Hypophosporous Acid, 50 after being down to 20mgKOH/g, vacuumizes, and vacuum tightness rises to-0.085Mpa gradually, is incubated 7 hours, and acid number drops to 0.5mgKOH/g, stopped reaction; Be cooled to 120 ℃, go out still, make the sulfonic acid type polyester polyol.Its performance perameter is as follows:
| Outward appearance | Acid number (mgKOH/g) | Hydroxyl value (mgKOH/g) | Water ratio (%) |
| The transparent glue of little Huang | 0.5 | 56 | 0.03 |
(2) height contains the sulfonic acid type Synthesis of Waterborne Polyurethane admittedly
Under nitrogen protection, 0.1 part of 20 parts of 4 parts of 40 parts of 5 parts of sulfonic acid type polyester polyols, polypropylene glycol ethers, ethylene glycol, the HDI of step (1) and Dibutyltin oxide at 85 ℃ of reaction 6h, are cooled to 40 ℃ and add water dispersion, obtain aqueous polyurethane dispersion.Its performance perameter is as follows:
| Outward appearance | Admittedly contain (%) | Particle diameter | Viscosity (cps) |
| The little indigo plant of white | 60 | 120 | 1300 |
Embodiment 3
(1) preparation of sulfonic acid type polyester polyol
Under nitrogen protection, with 32 parts of 5-sodium sulfo isophthalates, 130 part 1,6-hexylene glycol, 60 parts of toluene add and are equipped with in the straight four-hole bottle of agitator arm, temperature sensor, nitrogen and water-and-oil separator, are warming up to 170 ℃ of reactions 2 hours; Be warming up to 210 ℃ by 0.2 ℃/minute, be incubated 8 hours, after acid number is down to 5mgKOH/g, be cooled to 120 ℃; Add 100 parts of hexanodioic acids, slowly be warming up to 160 ℃ of insulations 2 hours, add 3 part 1,6-hexylene glycol, 0.15 part of Dibutyltin oxide; Slowly be warming up to 230 ℃ of reactions 4 hours, acid number is down to 0.05 part of the triphenyl phosphate ester of phosphorating behind the 10mgKOH/g, vacuumizes, and vacuum tightness rises to-0.1Mpa gradually, is incubated 8 hours, and acid number drops to 0.5mgKOH/g, stopped reaction; Be cooled to 140 ℃, go out still, make the sulfonic acid type polyester polyol.Its performance perameter is as follows:
| Outward appearance | Acid number (mgKOH/g) | Hydroxyl value (mgKOH/g) | Water ratio (%) |
| The transparent glue of little Huang | 0.5 | 55 | 0.03 |
(2) height contains the sulfonic acid type Synthesis of Waterborne Polyurethane admittedly
Under nitrogen protection; with 50 parts of 8 parts of sulfonic acid type polyester polyols, the PTMG (molecular weight 2000) of step (1), 1; 0.15 part of 2 parts of 6-hexylene glycol esters, 40 parts of TDI and Mono-n-butyltin are at 82 ℃ of reaction 5h; be cooled to 40 ℃ and add water dispersion, obtain aqueous polyurethane dispersion.Its performance perameter is as follows:
| Outward appearance | Admittedly contain (%) | Particle diameter | Viscosity (cps) |
| The little indigo plant of white | 60 | 119 | 1250 |
Should be understood that application of the present invention is not limited to above-mentioned giving an example, for those of ordinary skills, can be improved according to the above description or conversion that all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (8)
1. a sulfonic acid type polyester polyol is characterized in that, its molecular structural formula is as follows:
Wherein, R
1=(CH
2) x, R
2=
,
,
Or (CH
2) y, x=2,3,4,5 or 6, y=3,4 or 5.
2. sulfonic acid type polyester polyol according to claim 1 is characterized in that, according to the parts by weight meter, its composition of raw materials consists of:
28～52 parts of 5-sodium sulfo isophthalates, 110～180 parts of dibasic alcohol, 40～80 parts of solvents, 100～190 parts of diprotic acid, 0.05～0.15 part of catalyzer, 0.01～0.05 part in oxidation inhibitor.
3. sulfonic acid type polyester polyol according to claim 2 is characterized in that, described dibasic alcohol is ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol or their mixture; Described diprotic acid is Succinic Acid, pentanedioic acid, hexanodioic acid, phthalic acid, m-phthalic acid, terephthalic acid, phthalic anhydride or their mixture; Described catalyzer is Mono-n-butyltin, Dibutyltin oxide, dibutyl tin dilaurate, dibutyl tin acetate, titanium isopropylate or tetrabutyl titanate; Described solvent is diethylene glycol monobutyl ether, ethylene glycol monobutyl ether or dimethylbenzene; Described oxidation inhibitor is Hypophosporous Acid, 50, triphenylphosphate or four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester.
4. a sulfonic acid type aqueous polyurethane is characterized in that, described sulfonic acid type aqueous polyurethane raw material is formed and comprised arbitrary described sulfonic acid type polyester polyol as claim 1-3; The molecular structural formula of described sulfonic acid type aqueous polyurethane is as follows:
5. sulfonic acid type aqueous polyurethane according to claim 4 is characterized in that, according to the parts by weight meter, its composition of raw materials consists of:
5～10 parts of sulfonic acid type polyester polyols, 40～60 parts of polyether Glycols, 2～4 parts of small molecules dibasic alcohol, 20～40 parts of polyisocyanates, 0.05～0.15 part of catalyzer.
6. sulfonic acid type aqueous polyurethane according to claim 5 is characterized in that, described polyether Glycols is polypropylene glycol ether or PTMG; Described small molecules dibasic alcohol is ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol ester, TriMethylolPropane(TMP) or their mixture; Described polyisocyanates is TDI, HDI, IPDI or their mixture; Described catalyzer is tertiary amine catalyst or organic tin catalyzer.
7. the preparation method as the arbitrary described sulfonic acid type polyester polyol of claim 1-3 is characterized in that, may further comprise the steps:
Under protection of inert gas, 28～52 parts of 5-sodium sulfo isophthalates, 110～180 parts of dibasic alcohol and solvent are warming up to 150～170 ℃ of reactions 1～2 hour for 40～80 parts, be warming up to 190～210 ℃ then, be incubated 4～8 hours, after acid number is down to 5～10mgKOH/g, be cooled to 80～120 ℃; Add 100～190 parts of diprotic acid and slowly be warming up to 140～160 ℃ of insulations 1～2 hour, add 0.05～0.15 part of catalyzer, add 3～6 parts of dibasic alcohol; Slowly be warming up to 220～230 ℃ of reactions 3～4 hours, acid number adds 0.01～0.05 part in oxidation inhibitor after being down to 10～30mgKOH/g, vacuumizes, and is incubated 6～8 hours, and acid number drops to 0.5～5mgKOH/g, stopped reaction; Be cooled to 120～140 ℃.
8. the preparation method as claim 5 or 6 arbitrary described sulfonic acid type polyester polyols is characterized in that, may further comprise the steps:
Under protection of inert gas, at 80～85 ℃ of reaction 5～8h, cooling adds water dispersion with 0.05～0.15 part of 5～10 parts of sulfonic acid type polyester polyols, 40～60 parts of polyether Glycols, 2～4 parts of small molecules dibasic alcohol, 20～40 parts of polyisocyanates and catalyzer.
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| CN109180901A (en) * | 2018-08-23 | 2019-01-11 | 洛阳盛嘉新材料有限公司 | From delustring aqueous polyurethane and preparation method thereof |
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| CN1250452A (en) * | 1997-03-17 | 2000-04-12 | 陶氏化学公司 | Continuous process for preparing a polyurethane latex |
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| CN1250452A (en) * | 1997-03-17 | 2000-04-12 | 陶氏化学公司 | Continuous process for preparing a polyurethane latex |
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