CN108166261A - A kind of environment-friendly watertight washes waterproofing agent and preparation method thereof - Google Patents
A kind of environment-friendly watertight washes waterproofing agent and preparation method thereof Download PDFInfo
- Publication number
- CN108166261A CN108166261A CN201810083735.3A CN201810083735A CN108166261A CN 108166261 A CN108166261 A CN 108166261A CN 201810083735 A CN201810083735 A CN 201810083735A CN 108166261 A CN108166261 A CN 108166261A
- Authority
- CN
- China
- Prior art keywords
- hyper
- branched polyester
- waterproofing agent
- preparation
- ldi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The present invention provides a kind of environment-friendly watertights to wash waterproofing agent and preparation method thereof, it is characterised in that the waterproofing agent includes a kind of hyper-branched polyester modifier, and molecular formula is：
Description
Technical field
The invention belongs to textile auxiliary's final finishing fields, and in particular to a kind of environment-friendly watertight washes waterproofing agent and its system
Preparation Method.
Background technology
The key subjects of in the 21st century, facing mankind environmental protection.All environmentally harmful products all can be slowly substituted.
At present, the leading products of fluorine-containing water-proof aagent are still that the acrylic polymer of the Long carbon chain containing perfluor is (general in the market
All it is the perfluoroalkyl acrylate containing 8 carbon).With progress of research, people gradually have found the acrylic acid of perfluor Long carbon chain
Containing perfluorooctane sulfonyl compound (PFOS) and perfluoro caprylic acid ammonium compounds (PFOA) in esters polymer, and both objects
Matter be difficult to degrade (PFOS/PFOA is considered as one of organic pollution for being most difficult to degradation), bioaccumulation and environmental toxicity compared with
Seriously.Animal experiments show that PFOS can have an impact heredity, reproduction, development, liver crucian carp, immune and angiocarpy etc..In addition also have
People points out that PFOS is possible to carcinogenic.Persistence, toxicity and the bioaccumulation that PFOS/PFOA in 2002 is considered in the environment be
The significant problem of threatening environment and human health.
In western developed country, some policies and regulations are promulgated in succession.European Parliament limited the quantity to related PFOS in 2006
Relevant regulations are done.To 2015, own completely forbid in the U.S. used PFOS/PFOA.Due to relevant limitation, develop a kind of new
, without PFOS/PFOA, and the good fabric waterproofing agent of waterproof effect oneself become research hotspot in recent years.Especially easily drop
Solution, water-fastness water-proof aagent will be as new developing direction.
Although the country puts into effect corresponding policies and regulations not yet, C8 main products are also using, international to limit the use of
Certain influence certainly will be also generated to domestic market with disabling, the waterproofing agent of short carbon chain (as long as using C6 as the product of representative)
Researching and developing and putting goods on the market has been trend of the times.Some international chemical industry major companies, have had launched C6 waterproofing agent products.In addition without
Harmless, the environmental-friendly no fluoro water proofing agent of poison is also another direction, oneself is released without fluoro water proofing agent for German Wa Ke companies, although nothing
The characteristics of effect of fluoro water proofing agent is slightly worse compared to fluorine-containing water repellent, water-wash resistance is not also strong, but its is environmental-friendly is that the latter can not
It is equal to, it is believed that in the near future, no fluoro water proofing agent will be main product.
Invention content
The purpose of the present invention is to provide a kind of waterproofing agent of environment-friendly type, there is excellent waterproof effect and water-fast simultaneously
Wash performance.
The present invention is to implement to realize by following technology：
A kind of environment-friendly watertight washes waterproofing agent, it is characterised in that and the waterproofing agent includes a kind of hyper-branched polyester modifier,
Its molecular formula is：
Wherein A-OH is trimethylolpropane and 2,2- dihydroxymethyls
Hyper-branched polyester prepared by propionic acid reaction, the hydroxyl value of x+y≤A, x:Y is 8.4-30.8：3.6-13.2.
The environment-friendly watertight washes waterproofing agent also comprising fibrillation plant fiber, the fibrillation plant fiber with it is hyperbranched
The mass ratio 1 of polyester modification object:2-5, the avarage fiber diameter of shown fibrillation plant fiber is 50-100nm..
The present invention also provides the preparation methods that environment-friendly watertight washes waterproofing agent, include the following steps：
(1) trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1：9-1：41 molar ratio mixings, are warming up to 140-160
DEG C, argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, and 400-500Pa is decompressed to after reacting 2-3h,
The reaction was continued 2-3h stops decompression and being cooled to 40-60 DEG C, adds in a certain amount of acetone solution, then precipitates to obtain product through ether and surpass
Branched polyester；
(2) by lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10- at 40-45 DEG C
12h obtains semi-additive product LDI-HEA.
(3) hyper-branched polyester, succinic anhydride and the acetone that secondly step 1 is obtained stir and evenly mix, and are reacted at 90-95 DEG C
4-5h is cooled to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h, stops reaction, and product is precipitated through acetone ether, and vacuum is done
It is dry to obtain product.
Further, trimethylolpropane described in step 1 and 2,2- dihydromethyl propionic acid press 1：20 molar ratio mixings.
Further, hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios are 1 in step 3：8.4-30.8：3.6-
13.2
Further, hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios 1：16.1：6.9.
A-OH is that trimethylolpropane reacts the hyper-branched polyester prepared with 2,2- dihydromethyl propionic acids.The hyperbranched poly
Ester constantly carries out hyperbranched reaction, constantly extends away, shape according to the branching agent 2 of addition, the content of 2- dihydromethyl propionic acids
Into hyperbranched macromolecular.One of specific example is as follows：
But A-OH is not limited to the example, can be using trimethylolpropane as
Centronucleus, hyper-branched polyester of 2, the 2- dihydromethyl propionic acids for the arbitrary extension degree of branched monomer.
The reaction mechanism of step 1 is as follows：
It wherein can be according to the difference of n, so as to constantly extend hyper-branched polyester.
The reaction mechanism of step 3 is as follows：
Wherein, the hydroxyl value of x+y≤A.
Beneficial effects of the present invention：
(1) present invention provides a kind of preparation method of modified ultra-branching object, distinctive multi-active base group and reticular structure,
Make the waterproofing agent that there is excellent waterproof effect and water-wash resistance.
(2) while in the waterproofing agent of the present invention fibrillation plant fiber of nanoscale can also be added, is had abundant
Surface area and active group, can be effectively dispersed in waterproofing agent and be combined with modified ultra-branching object, in fabric surface
It during effect, can more effectively attach on the surface of fabric fibre, form more firm waterproof layer and increase the residence time, from
And improve waterproof rate；
(3) present invention because in preparation process free-floride remove fluorine-containing water repellent from and bring the harm such as PFOS/PFOA, while prepared
Also the harmful substances such as formaldehydeless are a waterproofing agents of new generation with environment-friendly advantage in journey and final finished.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
The preparation of fibrillation plant fiber：Sodium hydroxide solution is added in during NBKP is starched, is mixed, is warming up to 80 DEG C instead
After answering 1 hour, defibering obtains microfibril in 30 minutes under the screw speed of 2000rpm in addition twin shaft kneading machine after neutralization concentration
Vegetable-fibre slurry, by characterizing its average diameter as 86nm.
Implement 1
1. trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1 respectively：9 molar ratio mixings, are warming up to 140-160
DEG C, argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, and 400-500Pa is decompressed to after reacting 2-3h,
The reaction was continued 2-3h stops decompression and being cooled to 40-60 DEG C, adds in a certain amount of acetone solution, then precipitates to obtain product through ether and surpass
Branched polyester.
2. by lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10- at 40-45 DEG C
12h obtains semi-additive product LDI-HEA.
3. the hyper-branched polyester, succinic anhydride and a certain amount of acetone in step 1 stir and evenly mix, anti-at 90-95 DEG C
4-5h is answered, is cooled to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h, stopping reaction.Product is precipitated through acetone ether, vacuum
Dry hyper-branched polyester modifier.(hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios are 1：8.4：3.6)
Implement 2
1. trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1 respectively：9 molar ratio mixings, are warming up to 140-160
DEG C, argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, and 400-500Pa is decompressed to after reacting 2-3h,
The reaction was continued 2-3h stops decompression and being cooled to 40-60 DEG C, adds in a certain amount of acetone solution, then precipitates to obtain product through ether and surpass
Branched polyester.
2. by lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10- at 40-45 DEG C
12h obtains semi-additive product LDI-HEA.
3. the hyper-branched polyester, succinic anhydride and a certain amount of acetone in step 1 stir and evenly mix, anti-at 90-95 DEG C
4-5h is answered, is cooled to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h, stopping reaction.Product is precipitated through acetone ether, vacuum
Dry hyper-branched polyester modifier.(hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios are 1：6：6)
Implement 3
1. trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1 respectively：20 molar ratio mixings, are warming up to 140-160
DEG C, argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, and 400-500Pa is decompressed to after reacting 2-3h,
The reaction was continued 2-3h stops decompression and being cooled to 40-60 DEG C, adds in a certain amount of acetone solution, then precipitates to obtain product through ether and surpass
Branched polyester.
2. by lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10- at 40-45 DEG C
12h obtains semi-additive product LDI-HEA.
3. the hyper-branched polyester, succinic anhydride and a certain amount of acetone in step 1 stir and evenly mix, anti-at 90-95 DEG C
4-5h is answered, is cooled to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h, stopping reaction.Product is precipitated through acetone ether, vacuum
Dry hyper-branched polyester modifier.(hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios are 1：16.1：6.9)
Implement 4
1. trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1 respectively：20 molar ratio mixings, are warming up to 140-160
DEG C, argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, and 400-500Pa is decompressed to after reacting 2-3h,
The reaction was continued 2-3h stops decompression and being cooled to 40-60 DEG C, adds in a certain amount of acetone solution, then precipitates to obtain product through ether and surpass
Branched polyester.
2. by lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10- at 40-45 DEG C
12h obtains semi-additive product LDI-HEA.
3. the hyper-branched polyester, succinic anhydride and a certain amount of acetone in step 1 stir and evenly mix, anti-at 90-95 DEG C
4-5h is answered, is cooled to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h, stopping reaction.Product is precipitated through acetone ether, vacuum
Dry hyper-branched polyester modifier.(hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios are 1：11.5：11.5)
Implement 5
1. trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1 respectively：41 molar ratio mixings, are warming up to 140-160
DEG C, argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, and 400-500Pa is decompressed to after reacting 2-3h,
The reaction was continued 2-3h stops decompression and being cooled to 40-60 DEG C, adds in a certain amount of acetone solution, then precipitates to obtain product through ether and surpass
Branched polyester.
2. by lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10- at 40-45 DEG C
12h obtains semi-additive product LDI-HEA.
3. the hyper-branched polyester, succinic anhydride and a certain amount of acetone in step 1 stir and evenly mix, anti-at 90-95 DEG C
4-5h is answered, is cooled to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h, stopping reaction.Product is precipitated through acetone ether, vacuum
Dry hyper-branched polyester modifier.(hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios are 1：30.8：13.2)
Implement 6
1. trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1 respectively：41 molar ratio mixings, are warming up to 140-160
DEG C, argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, and 400-500Pa is decompressed to after reacting 2-3h,
The reaction was continued 2-3h stops decompression and being cooled to 40-60 DEG C, adds in a certain amount of acetone solution, then precipitates to obtain product through ether and surpass
Branched polyester.
2. by lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10- at 40-45 DEG C
12h obtains semi-additive product LDI-HEA.
3. the hyper-branched polyester, succinic anhydride and a certain amount of acetone in step 1 stir and evenly mix, anti-at 90-95 DEG C
4-5h is answered, is cooled to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h, stopping reaction.Product is precipitated through acetone ether, vacuum
Dry hyper-branched polyester modifier.(hyper-branched polyester, succinic anhydride and LDI-HEA molar ratios are 1：22：22)
6 kinds of hyper-branched polyester modifiers that above-mentioned implementation obtains are carried out to be re-dubbed waterproofing agent, reference standard AATCC is carried out
Waterproof test, then the testing water-proof performance after 10 standard water washings.
| Number | Waterproof effect | Waterproof effect after 10 washings |
| Embodiment 1 | 95 | 85 |
| Embodiment 2 | 95 | 80 |
| Embodiment 3 | 100 | 95+ |
| Embodiment 4 | 100 | 90+ |
| Embodiment 5 | 95 | 90 |
| Embodiment 6 | 95 | 85+ |
Embodiment 7
Hyper-branched polyester modifier prepared by embodiment 3 is with fibrillation plant fiber according to 3:1 mass ratio is answered
It is made into waterproofing agent.The waterproofing agent reference standard AATCC of embodiment 3 and embodiment 7 is subjected to waterproof test, then through 10,20 deutero-albumoses
Testing water-proof performance after quasi- water washing
| Number | Waterproof effect | Waterproof effect after 10 washings | Waterproof effect after 20 washings |
| Embodiment 3 | 100 | 95+ | 80+ |
| Embodiment 7 | 100 | 95+ | 90+ |
The present invention provides a kind of preparation method for overspending compound, distinctive multi-active base group and reticular structure, makes this anti-
Aqua has excellent waterproof effect and water-wash resistance.Comparative example 3 finds that addition fibrillation plant is fine with embodiment 7 simultaneously
Dimension can play better enhancing effect, and there is the hyper-branched polyester modifier with the present invention to cooperate with the modified effect of enhancing.
Finally it should be noted that present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.It is excellent
Embodiment is selected not limited the invention to the specific embodiments described there is no all details of detailed descriptionthe.Obviously, root
According to the content of this specification, can make many modifications and variations.This specification is chosen and specifically describes these embodiments, be in order to
The principle of the present invention and practical application are preferably explained, so as to which skilled artisan be enable to be best understood by and utilized
The present invention.The invention is limited only by the claims and the full scope thereof and equivalents thereof.
Claims (6)
1. a kind of environment-friendly watertight washes waterproofing agent, it is characterised in that the waterproofing agent includes a kind of hyper-branched polyester modifier,
Molecular formula is：
, wherein A-OH is trimethylolpropane and 2,2- dihydromethyl propionic acid
React the hyper-branched polyester prepared, the hydroxyl value of x+y≤A, x:Y is 8.4-30.8：3.6-13.2.
2. environment-friendly watertight according to claim 1 washes waterproofing agent, it is characterised in that the environment-friendly watertight washes waterproofing agent
Also comprising fibrillation plant fiber, the mass ratio 1 of the fibrillation plant fiber and hyper-branched polyester modifier:2-5, it is shown micro-
The avarage fiber diameter of fibrillation plant fiber is 50-100nm.
3. a kind of method for preparing environment-friendly watertight as described in claim 1 and washing waterproofing agent, includes the following steps：
（1）Trimethylolpropane and 2,2- dihydromethyl propionic acids are pressed 1：9-1：41 molar ratio mixings, are warming up to 140-160 DEG C,
Argon gas protection is lower to add in mass fraction 0.5-1% catalyst p-methyl benzenesulfonic acids, is decompressed to 400-500Pa after reacting 2-3h, continues
2-3h is reacted, stops decompression and being cooled to 40-60 DEG C, add in a certain amount of acetone solution, then through ether precipitates to obtain product hyperbranched
Polyester；
（2）By lysine diisocyanate and hydroxy-ethyl acrylate in molar ratio 1:1 mixing reacts 10-12h at 40-45 DEG C,
Obtain semi-additive product LDI-HEA；
（3）Hyper-branched polyester, succinic anhydride and the acetone that step 1 is obtained stir and evenly mix, and 4-5h is reacted at 90-95 DEG C, drop
Temperature stops reaction, product is precipitated through acetone ether, is dried in vacuo to obtain production to 45-50 DEG C of addition LDI-HEA, the reaction was continued 5-6h
Product.
4. preparation method according to claim 2, it is characterised in that trimethylolpropane described in step 1 and 2,2- dihydroxy
Methylpropanoic acid presses 1：20 molar ratio mixings.
5. preparation method according to claim 2, it is characterised in that hyper-branched polyester, succinic anhydride and LDI- in step 3
HEA molar ratios are 1：8.4-30.8：3.6-13.2.
6. preparation method according to claim 2, it is characterised in that hyper-branched polyester, succinic anhydride and LDI-HEA moles
Than 1：16.1：6.9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810049123 | 2018-01-18 | ||
| CN2018100491232 | 2018-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108166261A true CN108166261A (en) | 2018-06-15 |
Family
ID=62515793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810083735.3A Pending CN108166261A (en) | 2018-01-18 | 2018-01-29 | A kind of environment-friendly watertight washes waterproofing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108166261A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669202A (en) * | 2019-10-18 | 2020-01-10 | 南雄市沃太化工有限公司 | Light-curable aqueous hyperbranched resin and preparation method thereof |
| CN112252026A (en) * | 2020-09-23 | 2021-01-22 | 浙江桐星纺织科技发展股份有限公司 | Production process of environment-friendly phosphorus-based low-weight-gain flame-retardant fabric |
| CN112321909A (en) * | 2020-11-19 | 2021-02-05 | 侯光宇 | High-strength wear-resistant natural rubber composite material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297466A (en) * | 2006-04-28 | 2007-11-15 | Jsr Corp | Liquid curable resin composition |
| CN103030799A (en) * | 2013-01-05 | 2013-04-10 | 哈尔滨玻璃钢研究院 | Ternary core end epoxy hyperbranched polyester and preparation method thereof |
| CN103030798A (en) * | 2013-01-05 | 2013-04-10 | 哈尔滨玻璃钢研究院 | Quatenary core end epoxy hyperbranched polyester and preparation method thereof |
| CN103992485A (en) * | 2014-05-15 | 2014-08-20 | 东华大学 | Hyperbranched compound waterproofing agent and preparation method thereof |
| CN105064036A (en) * | 2015-09-08 | 2015-11-18 | 广东德美精细化工股份有限公司 | Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent |
| CN105378046A (en) * | 2013-07-12 | 2016-03-02 | 宝洁公司 | Structured fabric care compositions |
| CN105506992A (en) * | 2016-01-22 | 2016-04-20 | 河北宁纺集团有限责任公司 | Method for processing fluoride-free hydrostatic-pressure-resisting durable aterproof pure cotton canvas |
-
2018
- 2018-01-29 CN CN201810083735.3A patent/CN108166261A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297466A (en) * | 2006-04-28 | 2007-11-15 | Jsr Corp | Liquid curable resin composition |
| CN103030799A (en) * | 2013-01-05 | 2013-04-10 | 哈尔滨玻璃钢研究院 | Ternary core end epoxy hyperbranched polyester and preparation method thereof |
| CN103030798A (en) * | 2013-01-05 | 2013-04-10 | 哈尔滨玻璃钢研究院 | Quatenary core end epoxy hyperbranched polyester and preparation method thereof |
| CN105378046A (en) * | 2013-07-12 | 2016-03-02 | 宝洁公司 | Structured fabric care compositions |
| CN103992485A (en) * | 2014-05-15 | 2014-08-20 | 东华大学 | Hyperbranched compound waterproofing agent and preparation method thereof |
| CN105064036A (en) * | 2015-09-08 | 2015-11-18 | 广东德美精细化工股份有限公司 | Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent |
| CN105506992A (en) * | 2016-01-22 | 2016-04-20 | 河北宁纺集团有限责任公司 | Method for processing fluoride-free hydrostatic-pressure-resisting durable aterproof pure cotton canvas |
Non-Patent Citations (1)
| Title |
|---|
| 杨晓明等: "含羧基超支化聚酯丙烯酸酯的合成及其性能研究", 《涂料工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669202A (en) * | 2019-10-18 | 2020-01-10 | 南雄市沃太化工有限公司 | Light-curable aqueous hyperbranched resin and preparation method thereof |
| CN112252026A (en) * | 2020-09-23 | 2021-01-22 | 浙江桐星纺织科技发展股份有限公司 | Production process of environment-friendly phosphorus-based low-weight-gain flame-retardant fabric |
| CN112321909A (en) * | 2020-11-19 | 2021-02-05 | 侯光宇 | High-strength wear-resistant natural rubber composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108166261A (en) | A kind of environment-friendly watertight washes waterproofing agent and preparation method thereof | |
| US11359166B2 (en) | Fabric treatment composition | |
| CN105297426B (en) | A kind of fabric softener | |
| US2360477A (en) | Polymeric acetals and process of forming same | |
| CN111465733A (en) | Detergent | |
| CN101956322A (en) | Formaldehydeless permanent press finishing agent for fabric and preparation method and application thereof | |
| CN111690072B (en) | Preparation and application of polyaldehyde anti-crease finishing agent for cotton fabric | |
| CN102791922B (en) | Cellulosic fiber or cellulosic fiber product treatment method | |
| CN116641231A (en) | Multi-active-group reactive flame retardant and application thereof to durable flame-retardant finishing of protein fiber products | |
| Park et al. | Influence of glyoxal on preparation of poly (vinyl alcohol)/poly (acrylic acid) blend film | |
| CN114479061A (en) | Polyether amine chlorotriazine telechelic polymer tanning agent, and preparation method and application thereof | |
| CN109593898B (en) | Biomass-based reactive amphoteric retanning agent and preparation method thereof | |
| US4414277A (en) | Mixtures comprising fluorinated pyromellitate oligomers useful as surfactants and processes for the production and use thereof | |
| CN116676776A (en) | Multi-active-group efficient flame retardant and durable flame-retardant finishing method for cotton fabric thereof | |
| CN109610177A (en) | A kind of preparation method and application of cation type polyurethane esters of acrylic acid water repellent | |
| US3547986A (en) | Quaternary ammonium salt compositions for modifying cellulose materials | |
| US4446306A (en) | Oligomer-containing mixtures useful as fiber surface treating agents and processes for the production and use thereof | |
| CN105797643A (en) | Method for preparing non-ionic polyurethane Gemini surfactant | |
| CN110983784A (en) | Improved environment-friendly flame retardant composition and preparation method thereof | |
| CN106221551B (en) | Fire-retardant, waterproof and low VOC polyurethane coating preparation method | |
| CN110735325B (en) | Modified epoxy group POSS fluorine-free waterproof finishing agent and preparation method thereof | |
| JPS5869874A (en) | Ampho-ionic compound | |
| CN106380625A (en) | A process of preparing an ether-ester citrate plasticizer | |
| Franklin et al. | Recurable Durable-Press Fabrics: Part III: Textile, Chemical, and Recuring Properties of Fabrics Treated with DMDHEU and Polycarboxylic Acids | |
| CN109137521A (en) | A kind of preparation method of polybasic carboxylic acid crease-shedding finishing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180615 |
|
| RJ01 | Rejection of invention patent application after publication |