CN103012741B - Polyester-type cationic aqueous fluorinated polyurethane, preparation method and application thereof - Google Patents
Polyester-type cationic aqueous fluorinated polyurethane, preparation method and application thereof Download PDFInfo
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- CN103012741B CN103012741B CN201210500222.0A CN201210500222A CN103012741B CN 103012741 B CN103012741 B CN 103012741B CN 201210500222 A CN201210500222 A CN 201210500222A CN 103012741 B CN103012741 B CN 103012741B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004814 polyurethane Substances 0.000 title abstract description 30
- 229920002635 polyurethane Polymers 0.000 title abstract description 30
- 125000002091 cationic group Chemical group 0.000 title abstract 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 38
- 229920000728 polyester Polymers 0.000 claims description 38
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 33
- 239000011737 fluorine Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 20
- 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 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 12
- -1 polyethylene adipate Polymers 0.000 abstract 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 2
- 229920000921 polyethylene adipate Polymers 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000005457 ice water Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 14
- 150000001768 cations Chemical class 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000003556 assay Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyester-type cationic aqueous fluorinated polyurethane, a preparation method and application of the polyester-type cationic aqueous fluorinated polyurethane, wherein the polyester-type cationic aqueous fluorinated polyurethane consists of polyethylene adipate glycol ester, 1,6-hexamethylene diisocyanate tripolymer monofluoro alcohol adduct, a chain extender, a neutralizing agent, a catalyst and a thinner; the preparation method comprises the following steps of: dehydrating the polyethylene adipate glycol ester in a vacuum environment at 120 DEG C; filling nitrogen, adding the 1,6-hexamethylene diisocyanate tripolymer monofluoro alcohol adduct, uniformly mixing, raising the temperature to 85-90 DEG C; reacting for 2h, decreasing the temperature to 60 DEG C, adding the chain extender and the catalyst; continuing to react for 1h, adding the thinner; pouring in ice water which is added with the neutralizing agent, and shearing and emulsifying for 10min at a high speed of 1000r/min; and decompressing, distilling and separating the thinner to obtain the polyester-type cationic aqueous fluorinated polyurethane. The polyester-type cationic aqueous fluorinated polyurethane disclosed by the invention, applied to the leather finishing agent, can guarantee soft, natural and full appearance of the leather, and can improve the grade of the leather.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to cation-type water-thinned fluorochemical urethane of a kind of polyester type and preparation method thereof and the application in hide finishes.
Background technology
On the molecular chain of cation-type water-thinned polyurethane, with positive electricity, hydrophobic polyester, propenyl kind fabric fiber are had to good wetting property, be with a wide range of applications in fields such as weaving, leather and papermaking.
Current hide finishes mainly contains single-component cation-type water-thinned polyurethane and solvent borne polyurethane.Single-component cation-type water-thinned polyurethane is because it exists hydrophilic radical, therefore hardness, water tolerance and the solvent resistance of traditional single-component cation-type water-thinned polyurethane finishing agent do not reach the level of solvent borne polyurethane, and solvent borne polyurethane is owing to existing environmental issue on the verge of being replaced gradually.
Based on above background, the cation-type water-thinned polyurethane hide finishes of, excellent in abrasion resistance good in the urgent need to development water-tolerant, solvent resistance, mechanical property excellence, environment-friendly type, expands the range of application of hide finishes.
Summary of the invention
One of the object of the invention is in order to solve the technical problems such as hardness, water tolerance and the resistance to solvent of the contaminate environment of above-mentioned solvent borne polyurethane, traditional single-component cation-type water-thinned polyurethane be poor and provide a kind of performance to be better than single-component cation-type water-thinned polyurethane, approach solvent borne polyurethane but than the solvent borne polyurethane cation-type water-thinned fluorochemical urethane of polyester type of environmental protection more.
Two of the object of the invention provides the preparation method of the cation-type water-thinned fluorochemical urethane of above-mentioned polyester type.
The technical solution used in the present invention
The cation-type water-thinned fluorochemical urethane of a kind of polyester type, calculates by weight, and its composition and content are as follows:
Polyethylene glycol adipate 40-60 part
Hexamethylene diisocyanate tripolymer-fluorine alcohol affixture 100-120 part
Chainextender 0.2-5.0 part
Neutralizing agent 0.2-8.0 part
Catalyzer 0.02-1.0 part
Thinner 40-60 part
The number-average molecular weight of wherein said polyethylene glycol adipate is 2000g/mol;
Described hexamethylene diisocyanate tripolymer-fluorine alcohol affixture, parts by weight calculate, and its composition and content are as follows:
Hexamethylene diisocyanate tripolymer 100-120 part
4,4,5,5,5-Pentafluorobenzyl pentanol 1-3 part
Dibutyl tin laurate 0.6-1.0 part
Described chainextender is N methyldiethanol amine;
Described catalyzer is the mixture of dibutyl tin laurate, stannous octoate or dibutyl tin laurate and stannous octoate composition; Be preferably dibutyl tin laurate or stannous octoate;
Described neutralizing agent is the mixture of one or more compositions in oxyacetic acid, Glacial acetic acid and diacetyl oxide; Preferred oxyacetic acid or diacetyl oxide;
Described thinner is acetone or butanone.
The preparation method of the above-mentioned cation-type water-thinned fluorochemical urethane of polyester type, specifically comprises the steps:
(1), by hexamethylene diisocyanate tripolymer, 4,4,5,5,5-Pentafluorobenzyl pentanol and dibutyl tin laurate join in container, obtain hexamethylene diisocyanate tripolymer-fluorine alcohol affixture after reacting 3h under nitrogen protection at 80 DEG C;
(2), by polyethylene glycol adipate at 120 DEG C; under 720-760mmHg vacuum tightness, stir dehydration 1h; then under logical nitrogen, add 1 of step (1) gained; hexamethylene-diisocyanate tripolymer-fluorine alcohol affixture; after mixing, temperature is risen to 85～90 DEG C of left and right, after reaction 2h, be cooled to 60 DEG C, add chainextender and catalyzer; continue to add thinner after reaction 1h, obtain reaction solution;
Reaction solution obtained above is poured in the frozen water that is added with neutralizing agent, then in 1000r/min high speed shear emulsification 10min, underpressure distillation obtains the cation-type water-thinned fluorochemical urethane of polyester type after thinner is all deviate from;
Described neutralizing agent and frozen water are by weight calculating, i.e. neutralizing agent: frozen water is 1:100 ~ 200;
Described underpressure distillation controls temperature is 30 DEG C, vacuum tightness 750mmHg, mixing speed is to carry out under 60 ~ 90rpm, after all deviating to thinner till, take off in matrass without bubble, stop.
The cation-type water-thinned fluorochemical urethane of above-mentioned polyester type is for hide finishes.
Beneficial effect of the present invention
The cation water-based fluorochemical urethane of a kind of polyester type of the present invention, because ester carbonyl group can form numerous hydrogen bonds with H atom in hard section-HNCOO-structure, therefore has good solvent resistance.The existence of ester bond makes the rigidity reinforced of aqueous polyurethane, and aqueous polyurethane mechanical strength is strengthened.
Further; the cation water-based fluorochemical urethane of a kind of polyester type of the present invention in the C-F of molecular chain side chain group under self capillary driving when film forming; be easy to surface transport and enrichment; therefore there is good wear resistance, solvent resistance and water tolerance for hide finishes, thereby leather surface is effectively protected.The existence of C-F key has changed the micro phase separation structure of aqueous polyurethane, makes it to have higher tensile strength and elongation at break.
Further, the leather of processing through the cation-type water-thinned fluorochemical urethane of polyester type of the present invention, adopt the mensuration of standard GB/T/T19089-2003 rubber or plastic coat fabric abrasion resistance, 80,000 leathers after treatment that rub are unchanged, illustrate that thus the cation-type water-thinned fluorochemical urethane of polyester type of the present invention has good wear resistance; Adopt GB/T1040-1992 plastic tensile method for testing performance to detect, its tensile strength reaches 21.3 ~ 23.6MPa, elongation at break is 80 ~ 93%, higher than the tensile strength 6.72MPa of raw hide and 65% elongation at break, illustrate that thus the cation-type water-thinned fluorochemical urethane of polyester type of the present invention has good mechanical property respectively; Adopt sessile drop method to measure contact angle, its contact angle to water reaches 97-101 °, higher than 80 ° of raw hide, illustrates that thus the cation-type water-thinned fluorochemical urethane of polyester type of the present invention has good hydrophobicity; Adopt industry standard HGT 3856-2006 insullac paint film water-intake rate assay method to test, specific absorption is 3%, is better than 35% of raw hide, illustrates that thus the cation-type water-thinned fluorochemical urethane of polyester type of the present invention has good water tolerance.
In sum, the cation water-based fluorochemical urethane of polyester type of the present invention has good water tolerance, solvent resistance, wear resistance, mechanical property high, it can give leather softness, natural and plentiful outward appearance for hide finishes, promotes the advantage such as grade of leather.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the cation-type water-thinned fluorochemical urethane of polyester type of embodiment 1 gained.
Embodiment
Also by reference to the accompanying drawings the present invention is further set forth below by specific embodiment, but do not limit the present invention.
Various embodiments of the present invention raw material used is commercially available, and specification is chemical pure.
embodiment 1
The cation-type water-thinned fluorochemical urethane of a kind of polyester type, its one-tenth is grouped into that meter is as follows by weight:
40 parts of polyethylene glycol adipates
100 parts of hexamethylene diisocyanate tripolymer-fluorine alcohol affixtures
0.2 part of chainextender
0.2 part of neutralizing agent
0.02 part of catalyzer
40 parts of thinners
The number-average molecular weight of wherein said polyethylene glycol adipate is 2000g/mol;
Described chainextender is N methyldiethanol amine;
Described catalyzer is dibutyl tin laurate;
Described neutralizing agent is oxyacetic acid;
Described thinner is acetone;
It is as follows that described its one-tenth of hexamethylene diisocyanate tripolymer-fluorine alcohol affixture is grouped into by weight meter;
100 parts of hexamethylene diisocyanate tripolymers
1 part of 4,4,5,5,5-Pentafluorobenzyl pentanol
0.6 part of dibutyl tin laurate.
The preparation method of the above-mentioned cation-type water-thinned fluorochemical urethane of polyester type, specifically comprises that step is as follows:
(1), the preparation of hexamethylene diisocyanate tripolymer-fluorine alcohol affixture
Under nitrogen protection, in there-necked flask, add 100 parts of hexamethylene diisocyanate tripolymers and 0.6 part of dibutyl tin laurate, add 1 part 4,4,5,5,5-Pentafluorobenzyl pentanol, at 80 DEG C, react 2h, obtain hexamethylene diisocyanate tripolymer-fluorine alcohol affixture of faint yellow thickness;
(2), by above-mentioned 40 parts of polyethylene glycol adipates at 120 DEG C; under 750mmHg vacuum tightness, stir dehydration 1h; then under logical nitrogen, add 100 part 1; hexamethylene-diisocyanate tripolymer-fluorine alcohol affixture; after mixing, temperature is risen to 90 DEG C of left and right, after reaction 2h, be cooled to 60 DEG C, add 0.2 part of chainextender and 0.02 part of dibutyl tin laurate; after continuation reaction 1h, add the thinner acetone of 40 parts, obtain reaction solution;
The reaction solution of above-mentioned gained is poured into after the frozen water that is added with 0.2 part of neutralizing agent oxyacetic acid in 1000r/min high speed shear emulsification 10min, controlling temperature is 30 DEG C, vacuum tightness 750mmHg, mixing speed be under 60rpm, carry out underpressure distillation in matrass without bubble, illustrate that acetone all deviates from, obtain the cation-type water-thinned fluorochemical urethane of polyester type;
The above-mentioned frozen water that is added with neutralizing agent oxyacetic acid is by weight calculating, i.e. neutralizing agent oxyacetic acid: frozen water is 0.2:40.
The cation-type water-thinned fluorochemical urethane of polyester type of above-mentioned gained carries out Infrared spectroscopy by infrared chromatograph (Nicolet company of the U.S. 380 types), the infrared spectrogram of gained as shown in Figure 1, as can be seen from Figure 1,
3421 cm
-1be-NH-COO-structure in the stretching vibration absorption peak of N-H key;
2962 cm
-1be-CH
2the stretching vibration absorption peak of c h bond in structure;
2270 cm
-1near the stretching vibration absorption peak of correspondence-NCO group does not occur, illustrate-NCO complete reaction.
1718 cm
-1be-NH-COO-structure in the stretching vibration absorption peak of C=O key;
1560 cm
-1be-NH-COO-structure in the flexural vibration absorption peak of N-H key;
1230 cm
-1it is C-F key stretching vibration absorption peak;
1102 cm
-1place is the stretching vibration absorption peak of ehter bond C-O-C;
More than analyze and show, in the cation-type water-thinned fluorochemical urethane of polyester type, fluorine-containing alcohol has successfully been introduced on urethane side chain.
Leather is processed with the cation-type water-thinned fluorochemical urethane of polyester type of above-mentioned gained, leather after treatment: the mensuration that adopts standard GB/T/T 19089-2003 rubber or plastic coat fabric abrasion resistance, 80,000 leathers after treatment that rub are unchanged, are better than 20,000 times of common not fluorine-containing aqueous cation aqueous polyurethane hide finishes.Adopt GB/T1040-1992 plastic tensile method for testing performance to detect, its tensile strength reaches 21.3MPa, elongation at break is 93%, higher than the tensile strength 6.72MPa of raw hide and 65% elongation at break, be also better than the tensile strength 18MPa of similar not fluorine-containing aqueous cation aqueous polyurethane hide finishes and 75% elongation at break respectively.Adopt sessile drop method to measure contact angle, its contact angle to water reaches 101 °, higher than 80 ° of raw hide, is also better than 67 ° of similar not fluorine-containing aqueous cation aqueous polyurethane hide finishes, illustrates and has good hydrophobicity.Test by industry standard HGT3856-2006 insullac paint film water-intake rate assay method, specific absorption is 3%, is better than 35% of raw hide, is also better than 25% of similar not fluorine-containing aqueous cation aqueous polyurethane hide finishes.Partial properties meets or exceeds solvent type tensile strength 25MPa, and the abrasion resistance that elongation at break is 50%, 7 ten thousand time and the contact angle to water of 100 °, and environmental protection, have development potentiality.
embodiment 2
The cation-type water-thinned fluorochemical urethane of a kind of polyester type, its one-tenth is grouped into that meter is as follows by weight:
60 parts of polyethylene glycol adipates
120 parts of hexamethylene diisocyanate tripolymer-fluorine alcohol affixtures
5.0 parts of chainextenders
8.0 parts of neutralizing agents
1.0 parts of catalyzer
60 parts of thinners
The number-average molecular weight of wherein said polyethylene glycol adipate is 2000g/mol;
Described chainextender is N methyldiethanol amine;
Described catalyzer is stannous octoate;
Described neutralizing agent is Glacial acetic acid;
Described thinner is butanone;
It is as follows that described its one-tenth of hexamethylene diisocyanate tripolymer-fluorine alcohol affixture is grouped into by weight meter;
120 parts of hexamethylene diisocyanate tripolymers
3 parts of 4,4,5,5,5-Pentafluorobenzyl pentanols
1.0 parts of dibutyl tin laurates.
The preparation method of the above-mentioned cation-type water-thinned fluorochemical urethane of polyester type, specifically comprises that step is as follows:
(1), the preparation of hexamethylene diisocyanate tripolymer-fluorine alcohol affixture
Under nitrogen protection, in there-necked flask, add 120 parts of hexamethylene diisocyanate tripolymers and 1.0 parts of dibutyl tin laurates, add 3 part 4,4,5,5,5-Pentafluorobenzyl pentanol, at 80 DEG C, react 2h, obtain hexamethylene diisocyanate tripolymer-fluorine alcohol affixture of faint yellow thickness;
(2), by above-mentioned 60 parts of polyethylene glycol adipates at 120 DEG C, under 760mmHg vacuum tightness, stir dehydration 1h, then under logical nitrogen, add 120 part 1 of step (1) gained, hexamethylene-diisocyanate tripolymer-fluorine alcohol affixture, after mixing, temperature is risen to 90 DEG C of left and right, after reaction 2h, be cooled to 60 DEG C, add 5 parts of chainextenders and 1 part of dibutyl tin laurate, after continuation reaction 1h, add the thinner butanone of 60 parts, obtain reaction solution;
The reaction solution of above-mentioned gained is poured into after the frozen water that is added with 8 parts of neutralizing agent Glacial acetic acid in 1000r/min high speed shear emulsification 30min, controlling temperature is 30 DEG C, vacuum tightness 750mmHg, mixing speed be under 90rpm, carry out underpressure distillation in matrass without bubble, illustrate that butanone all deviates from, obtain
polyester typecation-type water-thinned fluorochemical urethane;
The above-mentioned frozen water that is added with neutralizing agent Glacial acetic acid is by weight calculating, i.e. neutralizing agent Glacial acetic acid: frozen water is 8:800.
Leather is processed with the cation-type water-thinned fluorochemical urethane of polyester type of above-mentioned gained, leather after treatment: the mensuration that adopts standard GB/T/T 19089-2003 rubber or plastic coat fabric abrasion resistance, 80,000 leathers after treatment that rub are unchanged, are better than 20,000 times of common not fluorine-containing aqueous cation aqueous polyurethane hide finishes.Adopt GB/T1040-1992 plastic tensile method for testing performance to detect, its tensile strength reaches 23.6MPa, elongation at break is 80%, higher than the tensile strength 6.72MPa of raw hide and 65% elongation at break, be also better than the tensile strength 18MPa of similar not fluorine-containing aqueous cation aqueous polyurethane hide finishes and 75% elongation at break respectively.Adopt sessile drop method to measure contact angle, its contact angle to water reaches 97 °, higher than 80 ° of raw hide, is also better than 67 ° of similar not fluorine-containing aqueous cation aqueous polyurethane hide finishes, illustrates and has good hydrophobicity.Test by industry standard HGT3856-2006 insullac paint film water-intake rate assay method, specific absorption is 3%, is better than 35% of raw hide, is also better than 25% of similar not fluorine-containing aqueous cation aqueous polyurethane hide finishes.Partial properties meets or exceeds solvent type tensile strength 25MPa, and the abrasion resistance that elongation at break is 50%, 7 ten thousand time and the contact angle to water of 100 °, and environmental protection, have development potentiality.
above said content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. a preparation method for the cation-type water-thinned fluorochemical urethane of polyester type, the cation-type water-thinned fluorochemical urethane of described polyester type, calculates by weight, and its raw material composition and content are as follows:
Polyethylene glycol adipate 40-60 part
Hexamethylene diisocyanate tripolymer-fluorine alcohol affixture 100-120 part
Chainextender 0.2-5.0 part
Neutralizing agent 0.2-8.0 part
Catalyzer 0.02-1.0 part
Thinner 40-60 part
The number-average molecular weight of wherein said polyethylene glycol adipate is 2000g/mol;
Described chainextender is N methyldiethanol amine;
Described catalyzer is the mixture of dibutyl tin laurate, stannous octoate or dibutyl tin laurate and stannous octoate composition;
Described neutralizing agent is the mixture of one or more compositions in oxyacetic acid, Glacial acetic acid and diacetyl oxide;
Described thinner is acetone or butanone;
Described hexamethylene diisocyanate tripolymer-fluorine alcohol affixture, calculates by weight, and its composition and content are as follows:
Hexamethylene diisocyanate tripolymer 100-120 part
4,4,5,5,5-Pentafluorobenzyl pentanol 1-3 part
Dibutyl tin laurate 0.6-1.0 part;
The preparation method of above-mentioned hexamethylene diisocyanate tripolymer-fluorine alcohol affixture, step is as follows:
By 4,4 of the hexamethylene diisocyanate tripolymer of 100-120 part, 1-3 part, the dibutyl tin laurate of 5,5,5-Pentafluorobenzyl pentanol and 0.6-1.0 part joins in container, under nitrogen protection, at 80 DEG C, react 3h and obtain hexamethylene diisocyanate tripolymer-fluorine alcohol affixture;
The preparation process that it is characterized in that the described cation-type water-thinned fluorochemical urethane of polyester type specifically comprises the steps:
(1), by hexamethylene diisocyanate tripolymer, 4,4,5,5,5-Pentafluorobenzyl pentanol and dibutyl tin laurate join in container, obtain hexamethylene diisocyanate tripolymer-fluorine alcohol affixture after reacting 3h under nitrogen protection at 80 DEG C;
(2), by polyethylene glycol adipate at 120 DEG C; under 720-760mmHg vacuum tightness, stir dehydration 1h; then under logical nitrogen, add 1 of step (1) gained; hexamethylene-diisocyanate tripolymer-fluorine alcohol affixture; after mixing, temperature is risen to 85～90 DEG C; after reaction 2h, be cooled to 60 DEG C and add chainextender and catalyzer, continue to add thinner after reaction 1h, obtain reaction solution;
Reaction solution obtained above is poured in the frozen water that is added with neutralizing agent, then in 1000r/min high speed shear emulsification 10min, underpressure distillation obtains the cation-type water-thinned fluorochemical urethane of polyester type after deviating from thinner.
2. the preparation method of the cation-type water-thinned fluorochemical urethane of a kind of polyester type as claimed in claim 1, is characterized in that the described cation-type water-thinned fluorochemical urethane of polyester type calculates by weight, and its composition and content are as follows:
40 parts of polyethylene glycol adipates
100 parts of hexamethylene diisocyanate tripolymer-fluorine alcohol affixtures
0.2 part of chainextender
0.2 part of neutralizing agent
0.02 part of catalyzer
40 parts of thinners
The number-average molecular weight of wherein said polyethylene glycol adipate is 2000g/mol;
Described chainextender is N methyldiethanol amine;
Described catalyzer is dibutyl tin laurate;
Described neutralizing agent is oxyacetic acid;
Described thinner is acetone;
Described hexamethylene diisocyanate tripolymer-fluorine alcohol affixture, calculates by weight, and its composition and content are as follows:
100 parts of hexamethylene diisocyanate tripolymers
1 part of 4,4,5,5,5-Pentafluorobenzyl pentanol
0.6 part of dibutyl tin laurate.
3. the preparation method of the cation-type water-thinned fluorochemical urethane of a kind of polyester type as claimed in claim 1, is characterized in that the described cation-type water-thinned fluorochemical urethane of polyester type calculates by weight, and its composition and content are as follows:
60 parts of polyethylene glycol adipates
120 parts of hexamethylene diisocyanate tripolymer-fluorine alcohol affixtures
5.0 parts of chainextenders
8.0 parts of neutralizing agents
1.0 parts of catalyzer
60 parts of thinners
The number-average molecular weight of wherein said polyethylene glycol adipate is 2000g/mol;
Described chainextender is N methyldiethanol amine;
Described catalyzer is stannous octoate;
Described neutralizing agent is Glacial acetic acid;
Described thinner is butanone;
Described hexamethylene diisocyanate tripolymer-fluorine alcohol affixture, calculates by weight, and its composition and content are as follows:
120 parts of hexamethylene diisocyanate tripolymers
3 parts of 4,4,5,5,5-Pentafluorobenzyl pentanols
1.0 parts of dibutyl tin laurates.
4. the preparation method of the cation-type water-thinned fluorochemical urethane of polyester type as claimed in claim 1, is characterized in that neutralizing agent and frozen water that step (2) is described calculate by weight, i.e. neutralizing agent: frozen water is 1:100 ~ 200.
5. the preparation method of the cation-type water-thinned fluorochemical urethane of polyester type as claimed in claim 1, is characterized in that it is 30 DEG C that temperature is controlled in the described underpressure distillation of step (2), vacuum tightness 750mmHg, and mixing speed is to carry out under 60 ~ 90rpm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0383365A2 (en) * | 1984-08-24 | 1990-08-22 | E.I. Du Pont De Nemours And Company | Modified fluorocarbonylimino biurets |
| US5565564A (en) * | 1989-12-29 | 1996-10-15 | E. I. Du Pont De Nemours And Company | Polyfluoro organic trimer compounds having urea linkage |
| CN101435159A (en) * | 2008-12-22 | 2009-05-20 | 陕西科技大学 | Cation type aqueous full fluorine polyurethane textile finishing agent and preparing method thereof |
| CN102115524A (en) * | 2009-12-30 | 2011-07-06 | 上海合达聚合物科技有限公司 | Fluorine-containing polyurethane and preparation method thereof |
-
2012
- 2012-11-30 CN CN201210500222.0A patent/CN103012741B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0383365A2 (en) * | 1984-08-24 | 1990-08-22 | E.I. Du Pont De Nemours And Company | Modified fluorocarbonylimino biurets |
| US5565564A (en) * | 1989-12-29 | 1996-10-15 | E. I. Du Pont De Nemours And Company | Polyfluoro organic trimer compounds having urea linkage |
| CN101435159A (en) * | 2008-12-22 | 2009-05-20 | 陕西科技大学 | Cation type aqueous full fluorine polyurethane textile finishing agent and preparing method thereof |
| CN102115524A (en) * | 2009-12-30 | 2011-07-06 | 上海合达聚合物科技有限公司 | Fluorine-containing polyurethane and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 李培枝等.水性全氟聚氨酯防水防油整理剂的制备及性能.《印染》.2009,(第13期), |
| 水性全氟聚氨酯防水防油整理剂的制备及性能;李培枝等;《印染》;20090701(第13期);第14-16页 * |
| 聚酯型阳离子水性聚氨酯乳液的合成研究;陆雪良等;《粘接》;20040410;第25卷(第02期);第19-22页 * |
| 陆雪良等.聚酯型阳离子水性聚氨酯乳液的合成研究.《粘接》.2004,第25卷(第02期), |
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