CN103030783A - Non-ionic aqueous fluorine-containing polyurethane and preparation method thereof - Google Patents
Non-ionic aqueous fluorine-containing polyurethane and preparation method thereof Download PDFInfo
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- CN103030783A CN103030783A CN2012105164456A CN201210516445A CN103030783A CN 103030783 A CN103030783 A CN 103030783A CN 2012105164456 A CN2012105164456 A CN 2012105164456A CN 201210516445 A CN201210516445 A CN 201210516445A CN 103030783 A CN103030783 A CN 103030783A
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Abstract
The invention discloses non-ionic aqueous fluorine-containing polyurethane and a preparation method thereof. The non-ionic aqueous fluorine-containing polyurethane consists of polyether N210, polyethylene glycol PEG2000, an isophorone diisocyanate tripolymer-fluorine alcohol additive product, a non-ionic chain extender, a catalyst, a diluent and ice water. The preparation method comprises two steps of preparation of the isophorone diisocyanate tripolymer-fluorine alcohol additive product and preparation of non-ionic aqueous fluorine-containing polyurethane. A non-ionic aqueous fluorine-containing polyurethane latex film is high in acid resistance, alkali resistance, salt tolerance and water tolerance, and has a contact angle to water of 93-99 degrees. Detected by a plastic tensile property test method of GB-T1040-1992, the non-ionic aqueous fluorine-containing polyurethane has tensile intensity up to 6.3-8.7MPa, and the breakage elongation ratio of 230-350 percent. The preparation method is mild in experiment conditions, easy to operate, and suitable for industrial production.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of non-ion aqueous fluorochemical urethane and preparation method thereof.
Background technology
Aqueous polyurethane refers to water-soluble or is scattered in the water and the urethane that forms.Because the polyaminoester emulsion water has replaced organic solvent to make medium, it has the advantages such as nontoxic, pollution-free.Wherein, non-ion aqueous polyurethane has preferably that acidproof, alkaline-resisting, salt stability has potential using value.
Document (Li Jian, Zhou Xiaotong. the preparation and property research of non-ionic type water-dispersible polyurethane. Chinese sizing agent, 2003,12(1): 26-29) report, adopting polyethers N210 is polyvalent alcohol, prepares negatively charged ion, positively charged ion and non-ionic type water-dispersible polyurethane with the ratio of NCO/ OH=1. 6, its mechanical property relatively under the equal preparation condition, find the 0.56MPa that only has of non-ionic type, and cationic and anionic be respectively 2.8MPa and 6.3MPa.
Document (Guo Peng, Cai Yi. the synthetic and character of non-ionic water polyurethane emulsion. Xi'an Technology University's journal, 2009,29 (5): 607-612) reported the specific absorption of the latex film of non-ionic water polyurethane, different with the mol ratio of-NCO group and-OH group prepolymerization reaction, specific absorption 48% ~ 60%.Higher specific absorption illustrates that its water tolerance is very poor.
This shows, still there are the technical problems such as poor mechanical property, water tolerance deficiency in non-ion aqueous polyurethane at present, has limited its further application.
Summary of the invention
One of the object of the invention is in order to solve the technical problems such as above-mentioned poor mechanical property, water tolerance deficiency and a kind of non-ion aqueous fluorochemical urethane is provided, and this non-ion aqueous fluorochemical urethane has good water tolerance and high strength high.
Two of the object of the invention provides the preparation method of above-mentioned a kind of non-ion aqueous fluorochemical urethane.
Technical scheme of the present invention
A kind of non-ion aqueous fluorochemical urethane calculates by weight, and its raw material composition and content are as follows:
Polyethers N210 20-40 part
Polyoxyethylene glycol PEG2000 40-60 part
Isophorone diisocyanate trimer-fluorine alcohol affixture 100-120 part
Non-ionic type chainextender 4-8 part
Catalyzer 0.02-1.0 part
Thinner 20-40 part
200 parts of frozen water
Wherein said non-ionic type chainextender is the TriMethylolPropane(TMP) poly glycol monomethyl ether;
Described catalyzer is the mixture that dibutyl tin laurate, stannous octoate or dibutyl tin laurate and stannous octoate form;
Described thinner is acetone or butanone;
Described isophorone diisocyanate trimer-fluorine alcohol affixture calculates by weight, and its raw material composition and content are as follows:
Isophorone diisocyanate trimer 100-120 part
2,2,2 tfifluoroethyl alcohol 10-15 part
Dibutyl tin laurate 0.6-1.0 part
The preparation method of above-mentioned non-ion aqueous fluorochemical urethane specifically comprises the steps:
(1), the preparation of isophorone diisocyanate trimer-fluorine alcohol affixture
Isophorone diisocyanate trimer, 2,2,2 tfifluoroethyl alcohol and dibutyl tin laurate are joined in the container, under nitrogen protection, at 80 ℃ of lower reaction 3h, obtain isophorone diisocyanate trimer-fluorine alcohol affixture;
(2), the preparation of non-ion aqueous fluorochemical urethane
Be 120 ℃ with polyethers N210, polyoxyethylene glycol PEG2000 in temperature, mixing speed is 30-60rpm, vacuum tightness is to stir dehydration 1h under the 720-760mmHg, then under logical nitrogen, add isophorone diisocyanate trimer-fluorine alcohol affixture, after mixing temperature is risen to about 85～90 ℃ reaction 2h; Then be cooled to 60 ℃, add non-ionic type chainextender and catalyzer, continue reaction 1h, add thinner in the reaction process, finally obtain system 1;
Behind 1000r/min high speed shear emulsification 10min, carry out underpressure distillation after pouring the system 1 of gained into frozen water, it is 30 ℃ that vacuum distillation process is preferably controlled temperature, pressure carries out under-the 755mmHg, underpressure distillation to the distillate without bubble, illustrate that thinner deviates from, namely obtain non-ion aqueous fluorochemical urethane.
Useful achievement of the present invention
Contain respectively polyoxyethylene glycol and TriMethylolPropane(TMP) poly glycol monomethyl ether in described a kind of non-ionic type fluorine-containing aqueous polyurethane master chain structure, by containing thereon a large amount of-CH
2CH
2The nonionic structure such as O-make the aqueous polyurethane paint film of preparation have preferably acidproof, alkaline-resisting, salt resistant character;
Because contain a large amount of C-F keys in its structure, C-F key bond energy is high, and the F atom can with hard section mutually in-H atom in the NHCOO-key forms a large amount of hydrogen bonds, thereby the mechanical property of aqueous polyurethane paint film improved greatly;
Further; because the C-F key in the made non-ion aqueous fluorochemical urethane structure migrates to material surface in solidification process; in the enrichment of film coated surface layer a large amount of fluoro-containing groups, thereby further provide acidproof, alkaline-resisting, salt tolerant, water-fast effective protection to non-ion aqueous fluorochemical urethane.
Further, therefore a kind of non-ionic type fluorine-containing aqueous polyurethane of gained of the present invention has the characteristics of environmental protection owing to not containing organic solvent.
Further, a kind of non-ionic type fluorine-containing aqueous polyurethane of gained of the present invention is through by GB 1763-1979(89) paint film chemical reagent resistance mensuration acidproof (HCl 10%) property, alkaline-resisting (NaOH 10%) property, the salt tolerance (NaCl 3% (weight) aqueous solution) of filming, immersion test through 96h, film intact, illustrate that non-ionic type fluorine-containing aqueous polyurethane latex film has good acid resistance, alkali resistance, salt tolerance.
Through press GB/T 1733-1993 paint film water tolerance assay method mensuration, through the immersion of 96h, do not find the phenomenons such as loss of gloss, variable color, foaming are wrinkling, come off, get rusty, illustrate that non-ionic type fluorine-containing aqueous polyurethane paint film has preferably water tolerance.Adopt sessile drop method to measure it to the contact angle of water, its contact angle to water reaches 93-99 °
Further detect through pressing GB/T1040-1992 plastic tensile method for testing performance, its tensile strength reaches 6.3 ~ 8.7MPa, and elongation at break is 230 ~ 350%, has shown that further it has higher mechanical property.
Further, non-ionic type fluorine-containing aqueous polyurethane emulsion of the present invention prepares through two-step reaction, and reaction conditions is gentle, is fit to suitability for industrialized production.
Description of drawings
The infrared spectrogram of the non-ion aqueous fluorochemical urethane of Fig. 1, embodiment 1 gained.
Embodiment
Below by embodiment the present invention is described in further detail, but do not limit the present invention.
The used raw material of various embodiments of the present invention is commercially available, and specification is chemical pure.
Embodiment 1
A kind of non-ion aqueous fluorochemical urethane calculates by weight, and its raw material composition and content are as follows:
20 parts of polyethers N210
40 parts of polyoxyethylene glycol PEG2000
100 parts of the pure affixtures of isophorone diisocyanate trimer-fluorine
4 parts of non-ionic type chainextenders
0.02 part of catalyzer
20 parts of thinners
200 parts of frozen water
Wherein said non-ionic type chainextender is the TriMethylolPropane(TMP) poly glycol monomethyl ether;
Described catalyzer is dibutyl tin laurate;
Described thinner is butanone;
Described isophorone diisocyanate trimer-fluorine alcohol affixture calculates by weight, and its raw material composition and content are as follows:
100 parts of isophorone diisocyanate trimers
10 parts of 2,2,2 tfifluoroethyl alcohols
0.6 part of dibutyl tin laurate.
The preparation method of above-mentioned a kind of non-ion aqueous fluorochemical urethane specifically comprises the steps:
(1), the preparation of isophorone diisocyanate trimer-fluorine alcohol affixture
Under nitrogen protection, add 100 parts of isophorone diisocyanate trimers and 0.3 part of dibutyl tin laurate in the there-necked flask, add 10 part 2,2,2-trifluoroethanol and remaining dibutyl tin laurate, 80 ℃ of lower reaction 2h namely get the isophorone diisocyanate trimer of faint yellow thickness-fluorine alcohol affixture;
(2), the preparation of non-ion aqueous fluorochemical urethane
Be 120 ℃ with 20 parts of polyethers N210,40 parts of polyoxyethylene glycol PEG2000 in temperature, rotating speed is 30rpm, vacuum tightness is to stir dehydration 1h under the 760mmHg, then under logical nitrogen, add 100 parts of the isophorone diisocyanate trimers of step (1) gained-fluorine alcohol affixture, after mixing temperature is risen to about 85 ℃ reaction 2h; Then be cooled to 60 ℃, add 0.02 part of 4 parts of non-ionic type chainextender TriMethylolPropane(TMP) poly glycol monomethyl ethers and dibutyl tin laurate, continue reaction 1h, add 20 parts of thinner butanone in the reaction process, finally obtain system 1;
The system 1 of gained is poured into after 200 parts of the frozen water in 1000r/min high speed shear emulsification 10min, the control temperature is 30 ℃, pressure for carry out under-the 755mmHg underpressure distillation to the distillate without bubble, illustrate that the thinner butanone all deviates from, namely obtain non-ion aqueous fluorochemical urethane.
The non-ion aqueous fluorochemical urethane of above-mentioned gained carries out Infrared spectroscopy by infrared chromatograph (U.S. Nicolet company 380 types), the infrared spectrogram of gained as shown in Figure 1, as can be seen from Figure 1,
3384 cm
-1Be-the NH-COO-structure in the stretching vibration absorption peak of N-H key;
2963 cm
-1Be-CH
2The stretching vibration absorption peak of c h bond in the structure;
2270 cm
-1Near the stretching vibration absorption peak of correspondence-NCO group do not occur, illustrate-NCO complete reaction.
1717 cm
-1Be-the NH-COO-structure in the stretching vibration absorption peak of C=O key;
1559 cm
-1Be-the NH-COO-structure in the flexural vibration absorption peak of N-H key;
1261 cm
-1It is C-F key stretching vibration absorption peak;
1096 cm
-1The place is the stretching vibration absorption peak of ehter bond C-O-C;
More than the analysis showed that, in the non-ion aqueous fluorochemical urethane ,-CH
2CH
2The O structure successfully has been incorporated on the master chain of urethane with PEG and TriMethylolPropane(TMP) poly glycol monomethyl ether, contains C-F key group and successfully is linked in the urethane.
The non-ion aqueous fluorochemical urethane of above-mentioned gained is through by GB 1763-1979(89) paint film chemical reagent resistance mensuration acidproof (HCl 10%) property, alkaline-resisting (NaOH 10%) property, the salt tolerance (NaCl 3% (weight) aqueous solution) of filming, immersion test through 96h, film intact, illustrate that non-ionic type fluorine-containing aqueous polyurethane latex film has good acid resistance, alkali resistance, salt tolerance.
The non-ion aqueous fluorochemical urethane of above-mentioned gained is measured through pressing GB/T 1733-1993 paint film water tolerance assay method, immersion through 96h, do not find that loss of gloss, variable color, foaming are wrinkling, the phenomenon such as come off, get rusty, illustrate that non-ionic type fluorine-containing aqueous polyurethane paint film has preferably water tolerance.
The non-ion aqueous fluorochemical urethane of above-mentioned gained is through adopting sessile drop method to measure it to the contact angle of water, and the result shows that its contact angle to water reaches 99 °.
The non-ion aqueous fluorochemical urethane of above-mentioned gained detects through pressing GB/T1040-1992 plastic tensile method for testing performance, and its tensile strength reaches 8.7MPa, and elongation at break is 230%, has shown that further it has higher mechanical property.
A kind of non-ion aqueous fluorochemical urethane calculates by weight, and its raw material composition and content are as follows:
40 parts of polyethers N210
60 parts of polyoxyethylene glycol PEG2000
120 parts of the pure affixtures of isophorone diisocyanate trimer-fluorine
8 parts of non-ionic type chainextenders
1.0 parts of catalyzer
40 parts of thinners
200 parts of frozen water
Wherein said non-ionic type chainextender is the TriMethylolPropane(TMP) poly glycol monomethyl ether;
Described catalyzer is stannous octoate;
Described thinner is acetone;
Described isophorone diisocyanate trimer-fluorine alcohol affixture calculates by weight, and its raw material composition and content are as follows:
120 parts of isophorone diisocyanate trimers
15 parts of 2,2,2 tfifluoroethyl alcohols
1.0 parts of dibutyl tin laurates.
The preparation method of above-mentioned a kind of non-ion aqueous fluorochemical urethane specifically comprises the steps:
(1), the preparation of isophorone diisocyanate trimer-fluorine alcohol affixture
Under nitrogen protection, add 100 parts of isophorone diisocyanate trimers and 0.5 part of dibutyl tin laurate in the there-necked flask, add 15 part 2,2,2-trifluoroethanol and remaining dibutyl tin laurate, 80 ℃ of lower reaction 2h namely get the isophorone diisocyanate trimer of faint yellow thickness-fluorine alcohol affixture;
(2), the preparation of non-ion aqueous fluorochemical urethane
Be 120 ℃ with 40 parts of polyethers N210,60 parts of polyoxyethylene glycol PEG2000 in temperature, rotating speed is 60rpm, vacuum tightness is to stir dehydration 1h under the 720mmHg, then under logical nitrogen, add 120 parts of the isophorone diisocyanate trimers of step (1) gained-fluorine alcohol affixture, after mixing temperature is risen to about 90 ℃ reaction 2h; Then be cooled to 60 ℃, add 1.0 parts in the inferior tin of 8 parts of the non-TriMethylolPropane(TMP) poly glycol monomethyl ethers of non-ionic type chainextender and octoate catalyst, continue reaction 1h, add 40 parts of thinner acetone in the reaction process, finally obtain system 1;
The system 1 of gained is poured into after 200 portions of frozen water behind 1000r/min high speed shear emulsification 10min, the control temperature is 30 ℃, pressure for-755mmHg carry out underpressure distillation to the distillate without bubble, illustrate that thinner acetone all deviates from, namely obtain non-ion aqueous fluorochemical urethane.
The non-ion aqueous fluorochemical urethane of above-mentioned gained is through by GB 1763-1979(89) paint film chemical reagent resistance mensuration acidproof (HCl 10%) property, alkaline-resisting (NaOH 10%) property, the salt tolerance (NaCl 3% (weight) aqueous solution) of filming, immersion test through 96h, film intact, illustrate that non-ionic type fluorine-containing aqueous polyurethane latex film has good acid resistance, alkali resistance, salt tolerance.
The non-ion aqueous fluorochemical urethane of above-mentioned gained is measured through pressing GB/T 1733-1993 paint film water tolerance assay method, immersion through 96h, do not find that loss of gloss, variable color, foaming are wrinkling, the phenomenon such as come off, get rusty, illustrate that non-ionic type fluorine-containing aqueous polyurethane paint film has preferably water tolerance.
The non-ion aqueous fluorochemical urethane of above-mentioned gained is through adopting sessile drop method to measure it to the contact angle of water, and the result shows that its contact angle to water reaches 93 °.
The non-ion aqueous fluorochemical urethane of above-mentioned gained detects through pressing GB/T1040-1992 plastic tensile method for testing performance, and its tensile strength reaches 6.3MPa, and elongation at break is 350%, has shown that further it has higher mechanical property.
Described content only is 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 non-ion aqueous fluorochemical urethane is characterized in that calculating by weight, and its raw material composition and content are as follows:
Polyethers N210 20-40 part
Polyoxyethylene glycol PEG2000 40-60 part
Isophorone diisocyanate trimer-fluorine alcohol affixture 100-120 part
Non-ionic type chainextender 4-8 part
Catalyzer 0.02-1.0 part
Thinner 20-40 part
200 parts of frozen water
Wherein said non-ionic type chainextender is the TriMethylolPropane(TMP) poly glycol monomethyl ether;
Described catalyzer is the mixture that dibutyl tin laurate, stannous octoate or dibutyl tin laurate and stannous octoate form;
Described thinner is acetone or butanone;
Described isophorone diisocyanate trimer-fluorine alcohol affixture calculates by weight, and its raw material composition and content are as follows:
Isophorone diisocyanate trimer 100-120 part
2,2,2 tfifluoroethyl alcohol 10-15 part
Dibutyl tin laurate 0.6-1.0 part;
The preparation of described isophorone diisocyanate trimer-fluorine alcohol affixture; be about to 100-120 part isophorone diisocyanate trimer, 10-15 part 2; 2; the dibutyl tin laurate of 2-trifluoroethanol and 0.6-1.0 part joins in the container; under nitrogen protection; at 80 ℃ of lower reaction 3h, obtain isophorone diisocyanate trimer-fluorine alcohol affixture.
2. a kind of non-ion aqueous fluorochemical urethane as claimed in claim 1 is characterized in that calculating by weight, and its raw material composition and content are as follows:
20 parts of polyethers N210
40 parts of polyoxyethylene glycol PEG2000
100 parts of the pure affixtures of isophorone diisocyanate trimer-fluorine
4 parts of non-ionic type chainextenders
20 parts of thinners
0.02 part of catalyzer
200 parts of frozen water
Wherein said non-ionic type chainextender is the TriMethylolPropane(TMP) poly glycol monomethyl ether;
Described catalyzer is dibutyl tin laurate;
Described thinner is butanone;
Described isophorone diisocyanate trimer-fluorine alcohol affixture calculates by weight, and its raw material composition and content are as follows:
100 parts of isophorone diisocyanate trimers
10 parts of 2,2,2 tfifluoroethyl alcohols
0.6 part of dibutyl tin laurate.
3. a kind of non-ion aqueous fluorochemical urethane as claimed in claim 1 is characterized in that calculating by weight, and its raw material composition and content are as follows:
40 parts of polyethers N210
60 parts of polyoxyethylene glycol PEG2000
120 parts of the pure affixtures of isophorone diisocyanate trimer-fluorine
8 parts of non-ionic type chainextenders
1.0 parts of catalyzer
40 parts of thinners
200 parts of frozen water
Wherein said non-ionic type chainextender is the TriMethylolPropane(TMP) poly glycol monomethyl ether;
Described catalyzer is stannous octoate;
Described thinner is acetone;
Described isophorone diisocyanate trimer-fluorine alcohol affixture calculates by weight, and its raw material composition and content are as follows:
120 parts of isophorone diisocyanate trimers
15 parts of 2,2,2 tfifluoroethyl alcohols
1.0 parts of dibutyl tin laurates.
4. such as the preparation method of claim 1,2 or 3 described non-ion aqueous fluorochemical urethanes, it is characterized in that specifically comprising the steps:
(1), the preparation of isophorone diisocyanate trimer-fluorine alcohol affixture
Isophorone diisocyanate trimer, 2,2,2 tfifluoroethyl alcohol and dibutyl tin laurate are joined in the container, under nitrogen protection, at 80 ℃ of lower reaction 3h, obtain isophorone diisocyanate trimer-fluorine alcohol affixture;
(2), the preparation of non-ion aqueous fluorochemical urethane
Be 120 ℃ with polyethers N210, polyoxyethylene glycol PEG2000 in temperature, mixing speed is 30-60rpm, vacuum tightness is to stir dehydration 1h under the 720-760mmHg, then under logical nitrogen, add isophorone diisocyanate trimer-fluorine alcohol affixture, after mixing temperature is risen to about 85～90 ℃ reaction 2h; Then be cooled to 60 ℃, add non-ionic type chainextender and catalyzer, continue reaction 1h, add thinner in the reaction process, finally obtain system 1;
With the system 1 of gained pour into after the frozen water behind 1000r/min high speed shear emulsification 10min underpressure distillation to the distillate without bubble, namely obtain non-ion aqueous fluorochemical urethane.
5. the preparation method of non-ion aqueous fluorochemical urethane as claimed in claim 4 is characterized in that it is 30 ℃ that temperature is namely controlled in the underpressure distillation described in the step (2), and pressure carries out under-the 755mmHg.
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Cited By (5)
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| CN106674463A (en) * | 2017-02-08 | 2017-05-17 | 上海金狮化工有限公司 | Polyurethane pigment dispersing agent and method for preparing same |
| CN108586687A (en) * | 2018-03-26 | 2018-09-28 | 四川大学 | A kind of preparation method of the fluorine-containing short chain surfactants of two blocks nonionic polyurethane |
| CN109929090A (en) * | 2019-03-12 | 2019-06-25 | 上海应用技术大学 | A kind of water-base resin fluorochemical and its preparation and application |
| CN110404296A (en) * | 2019-08-02 | 2019-11-05 | 广州大学 | A kind of super wetability water-oil separating material and the preparation method and application thereof |
| CN110862508A (en) * | 2019-11-27 | 2020-03-06 | 陕西科技大学 | Preparation method of triazine-based fluorine-containing chain extender modified polyurethane emulsion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674463A (en) * | 2017-02-08 | 2017-05-17 | 上海金狮化工有限公司 | Polyurethane pigment dispersing agent and method for preparing same |
| CN108586687A (en) * | 2018-03-26 | 2018-09-28 | 四川大学 | A kind of preparation method of the fluorine-containing short chain surfactants of two blocks nonionic polyurethane |
| CN109929090A (en) * | 2019-03-12 | 2019-06-25 | 上海应用技术大学 | A kind of water-base resin fluorochemical and its preparation and application |
| CN110404296A (en) * | 2019-08-02 | 2019-11-05 | 广州大学 | A kind of super wetability water-oil separating material and the preparation method and application thereof |
| CN110862508A (en) * | 2019-11-27 | 2020-03-06 | 陕西科技大学 | Preparation method of triazine-based fluorine-containing chain extender modified polyurethane emulsion |
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Inventor after: Yu Xiangqiang Inventor before: Zhang Yingqiang Inventor before: Li Ye Inventor before: Wu Qin Inventor before: Shen Bingying Inventor before: Shi Wen Inventor before: Liu Yueting Inventor before: Jiang Yuyun |
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Effective date of registration: 20160303 Address after: Guangdong province Zhongshan City Peace Village 528425 Dongfeng Town East Road (Liang Jianming building) Patentee after: Zhongshan City Dongfeng Town, Ocean Sports plastic material factory Address before: 200235 Xuhui District, Caobao Road, No. 120, Patentee before: Shanghai Institute of Technology |
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