CN110498896A - A kind of organic-silicon-modified water for synthetic leather rubs auxiliary agent and preparation method thereof - Google Patents
A kind of organic-silicon-modified water for synthetic leather rubs auxiliary agent and preparation method thereof Download PDFInfo
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- CN110498896A CN110498896A CN201910820573.1A CN201910820573A CN110498896A CN 110498896 A CN110498896 A CN 110498896A CN 201910820573 A CN201910820573 A CN 201910820573A CN 110498896 A CN110498896 A CN 110498896A
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
-
- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of organic-silicon-modified water for synthetic leather and rubs auxiliary agent, which includes following components: polyether-containing aminopolysiloxane, epoxy silicon oil, water-miscible organic solvent, polyisocyanates, deionized water, the chain extender containing carboxyl, neutralizer, amine chain extender and catalyst.The auxiliary agent improves the performance of waterborne polyurethane resin using two kinds of ingredients of amino modified polyether silicone and epoxy silicon oil, hence it is evident that improves the adhesive force for synthetic leather surface, can keep feel for a long time.
Description
Technical field
The present invention relates to a kind of use for synthetic leather inorganic agents, and in particular, to a kind of organic-silicon-modified water for synthetic leather
Auxiliary agent is rubbed, present invention simultaneously relates to the preparation methods that the organic-silicon-modified water rubs auxiliary agent.
Background technique
It is mainly the inorganic agent for including amido silicon oil or modified amino silicon oil that use for synthetic leather water currently on the market, which rubs auxiliary agent,.
For this inorganic agent using organosilicon as main support, it is obvious that water rubs rear submissive effect, but is not able to maintain the persistence of feel, especially after
Phase multiple clear water can lose feel after rubbing completely.Therefore, it still needs to find at the synthetic leather of the feel after water capable of being kept to rub for a long time
Manage agent.
Summary of the invention
For the above-mentioned deficiency of the prior art, the present invention provides a kind of organic-silicon-modified water for synthetic leather and rubs auxiliary agent.
The auxiliary agent improves the performance of waterborne polyurethane resin using two kinds of ingredients of amino modified polyether silicone and epoxy silicon oil, hence it is evident that mentions
High adhesive force of the auxiliary agent for synthetic leather surface, can keep feel for a long time.
According to an aspect of the present invention, a kind of organic-silicon-modified water for synthetic leather is provided and rubs auxiliary agent, comprising with the following group
Point: polyether-containing aminopolysiloxane, epoxy silicon oil, water-miscible organic solvent, isocyanates, deionized water, the chain extension containing carboxyl
Agent, neutralizer, amine chain extender and catalyst.
According to one embodiment of present invention, the proportion of each component is as follows: polyether-containing aminopolysiloxane 4-12 parts by weight, ring
Oxygen silicone oil 6-8 parts by weight, water-miscible organic solvent 8-15 parts by weight, isocyanates 10-20 parts by weight, deionized water 40-70 weight
It measures part, the chain extender 5-8 parts by weight containing carboxyl, neutralizer 0.5-1 parts by weight, amine chain extender 0.1-0.3 parts by weight and urges
Agent 0.5-1 parts by weight.
According to one embodiment of present invention, the water-miscible organic solvent is dimethylformamide.
According to one embodiment of present invention, the isocyanates is isophorone diisocyanate, toluene diisocynate
Ester, methyl diphenylene diisocyanate or polyisocyanates.
According to one embodiment of present invention, the chain extender containing carboxyl is 2,2- dihydromethyl propionic acid.
According to one embodiment of present invention, the neutralizer is triethylamine or ammonium hydroxide.
According to one embodiment of present invention, the amine chain extender is ethylenediamine.
According to one embodiment of present invention, the catalyst is organic bismuth catalyst.
According to another aspect of the present invention, provide it is a kind of be used to prepare the above-mentioned organic-silicon-modified water for synthetic leather and rub help
The method of agent, this method comprise the steps of
(1) reaction raw materials are weighed in proportion；
(2) polymerization reaction: weighed epoxy silicon oil, isocyanates, catalyst are placed in reaction vessel, predetermined first
Thermotonus 1-2 hours；
(3) chain extension is handled: weighed polyether-containing aminopolysiloxane being added into reaction vessel, water-miscible organic solvent, contains
There is the chain extender of carboxyl, reacts qualified to measured NCO% in the second predetermined temperature；
(4) decentralized processing: adding neutralizer into reaction vessel, reacts 5-15 minutes, in the case where high speed dispersion to
Deionized water emulsification is wherein imported, is added later through water-reducible amine chain extender, is reacted 10-30 minutes, obtain modified water
Property polyurethane resin.
According to one embodiment of present invention, first predetermined temperature is 60-70 DEG C, and second predetermined temperature is
70-80℃。
Organic-silicon-modified water disclosed in this invention for synthetic leather rub auxiliary agent and preparation method thereof can obtain it is following
Multiple beneficial effect:
(1) polyether-containing aminopolysiloxane is used, polyether-modified amido silicon oil has self-emulsifying ability, amino therein
It can interact with carboxyl, the hydroxyl of fiber surface, improve aligning for fiber surface, reduce interfibrous friction system
Number makes synthetic leather possess soft, Lubricity.
(2) functional groups such as the amino of the epoxy group in epoxy silicon oil and fiber, carboxyl, hydroxyl form covalent bond, with fiber
Firm connection, hence it is evident that enhance the wash durability of synthetic leather.
(3) in addition, the organic-silicon-modified water for synthetic leather of the invention rubs auxiliary agent, also to significantly improve synthetic leather submissive
The persistence of feel, compared with the single silicon oil modified auxiliary agent containing isodose, the softness of the auxiliary agent treated synthetic leather
Property and persistence all significantly improve, this may be due to there is PART EPOXY base also and in amido silicon oil in used epoxy silicon oil
Amino interaction, further improve the binding ability of amido silicon oil and fiber, keep its flexibility more longlasting.Moreover, by
It has both accessed in polyurethane structural in polyether-modified amido silicon oil and epoxy silicon oil, has been formed by later with latex composite compounding
Modified additive is compared, and the modified water of the application rubs auxiliary agent more resistant to washing.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer with reference to specific embodiments to this
Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, and does not have to
It is of the invention in limiting.
Embodiment 1
Each substance: 4 parts by weight of polyether-containing aminopolysiloxane, 8 parts by weight of epoxy silicon oil, dimethyl is weighed by following weight ratio
8 parts by weight of formamide, 10 parts by weight of isophorone diisocyanate, 40 parts by weight of deionized water, 5 weight of 2,2- dihydromethyl propionic acid
Measure part, 0.5 parts by weight of 0.5 parts by weight of triethylamine, 0.1 parts by weight of ethylenediamine and organic bismuth catalyst.
Weighed epoxy silicon oil, isophorone diisocyanate, organic bismuth catalyst are placed in reaction vessel, at 60 DEG C
Reaction 2 hours.
Weighed polyether-containing aminopolysiloxane, dimethylformamide, 2,2- dihydromethyl propionic acid are added into reaction vessel,
About 2 hours are reacted at 70 DEG C to measured NCO% qualification.
Triethylamine is added into reaction vessel again, reacts 5 minutes, imports deionization thereto in the case where high speed dispersion
Water emulsification is added later through water-reducible ethylenediamine, reacts 10 minutes, obtain modified waterborne polyurethane resin.
Embodiment 2
Each substance: 8 parts by weight of polyether-containing aminopolysiloxane, 7 parts by weight of epoxy silicon oil, dimethyl is weighed by following weight ratio
10 parts by weight of formamide, 14 parts by weight of isophorone diisocyanate, 50 parts by weight of deionized water, 2,2- dihydromethyl propionic acid 6
Parts by weight, 0.7 parts by weight of 0.8 parts by weight of triethylamine, 0.15 parts by weight of ethylenediamine and organic bismuth catalyst.
Weighed epoxy silicon oil, isophorone diisocyanate, organic bismuth catalyst are placed in reaction vessel, at 66 DEG C
Reaction 1.8 hours.
Weighed polyether-containing aminopolysiloxane, dimethylformamide, 2,2- dihydromethyl propionic acid are added into reaction vessel,
About 1.8 hours are reacted at 73 DEG C to measured NCO% qualification.
Add triethylamine into reaction vessel again, react 10 minutes, imported thereto in the case where high speed dispersion go from
Sub- water emulsification is added later through water-reducible ethylenediamine, reacts 20 minutes, obtain modified waterborne polyurethane resin.
Embodiment 3
Each substance: 10 parts by weight of polyether-containing aminopolysiloxane, 7 parts by weight of epoxy silicon oil, diformazan is weighed by following weight ratio
12 parts by weight of base formamide, 18 parts by weight of isophorone diisocyanate, 60 parts by weight of deionized water, 2,2- dihydromethyl propionic acid
7 parts by weight, 0.9 parts by weight of 0.8 parts by weight of triethylamine, 0.2 parts by weight of ethylenediamine and organic bismuth catalyst.
Weighed epoxy silicon oil, isophorone diisocyanate, organic bismuth catalyst are placed in reaction vessel, at 68 DEG C
Reaction 1.5 hours.
Weighed polyether-containing aminopolysiloxane, dimethylformamide, 2,2- dihydromethyl propionic acid are added into reaction vessel,
About 1.9 hours are reacted at 78 DEG C to measured NCO% qualification.
Add triethylamine into reaction vessel again, react 12 minutes, imported thereto in the case where high speed dispersion go from
Sub- water emulsification is added later through water-reducible ethylenediamine, reacts 30 minutes, obtain modified waterborne polyurethane resin.
Embodiment 4
Each substance: 12 parts by weight of polyether-containing aminopolysiloxane, 6 parts by weight of epoxy silicon oil, diformazan is weighed by following weight ratio
15 parts by weight of base formamide, 20 parts by weight of isophorone diisocyanate, 70 parts by weight of deionized water, 2,2- dihydromethyl propionic acid
8 parts by weight, 1 parts by weight of 1 parts by weight of triethylamine, 0.3 parts by weight of ethylenediamine and organic bismuth catalyst.
Weighed epoxy silicon oil, isophorone diisocyanate, organic bismuth catalyst are placed in reaction vessel, at 70 DEG C
Reaction 1 hour.
Weighed polyether-containing aminopolysiloxane, dimethylformamide, 2,2- dihydromethyl propionic acid are added into reaction vessel,
About 1.6 hours are reacted at 80 DEG C to measured NCO% qualification.
Add triethylamine into reaction vessel again, react 15 minutes, imported thereto in the case where high speed dispersion go from
Sub- water emulsification is added later through water-reducible ethylenediamine, reacts 30 minutes, obtain modified waterborne polyurethane resin.
In order to study the influence of the silicone oil of two-component and one-component for the performance of auxiliary agent, following implementation has also been carried out
Example.
Comparative example 1
The embodiment is substantially the same manner as Example 2, and difference is only that the embodiment does not use polyether-containing aminopolysiloxane,
But the epoxy silicon oil of 15 parts by weight is used.
Comparative example 2
The embodiment is substantially the same manner as Example 2, and difference is only that the embodiment does not use epoxy silicon oil, but uses
The polyether-containing aminopolysiloxanes of 15 parts by weight.
The technical performance index of inorganic agent prepared by the various embodiments described above is shown in Table 1:
Feel test, washability test and hydrophily is carried out to the synthetic leather of the inorganic agent processing Jing Guo each embodiment to survey
Examination, the results are shown in Table 2:
The above test result shows to rub its durability of auxiliary agent through the silicon oil modified water of two kinds of components and feel is better than list
The performance of the silicon oil modified auxiliary agent of one component has synergistic effect between two kinds of ingredients, therefore the auxiliary agent can improve synthesis
Remove from office the comprehensive performance of many aspects.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as.It should be pointed out that for those of ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection model of the invention
It encloses.
Claims (10)
1. a kind of organic-silicon-modified water for synthetic leather rubs auxiliary agent, which is characterized in that include following components: polyether modified amino
Silicone oil, epoxy silicon oil, water-miscible organic solvent, isocyanates, deionized water, the chain extender containing carboxyl, neutralizer, amine expand
Chain agent and catalyst.
2. the organic-silicon-modified water according to claim 1 for synthetic leather rubs auxiliary agent, which is characterized in that each component is matched
Than as follows: polyether-containing aminopolysiloxane 4-12 parts by weight, epoxy silicon oil 6-8 parts by weight, water-miscible organic solvent 8-15 parts by weight,
Isocyanates 10-20 parts by weight, deionized water 40-70 parts by weight, the chain extender 5-8 parts by weight containing carboxyl, neutralizer 0.5-1
Parts by weight, amine chain extender 0.1-0.3 parts by weight and catalyst 0.5-1 parts by weight.
3. the organic-silicon-modified water according to claim 1 for synthetic leather rubs auxiliary agent, which is characterized in that the water solubility
Organic solvent is dimethylformamide.
4. the organic-silicon-modified water according to claim 1 for synthetic leather rubs auxiliary agent, which is characterized in that the isocyanic acid
Ester is isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or polyisocyanates.
5. the organic-silicon-modified water according to claim 1 for synthetic leather rubs auxiliary agent, which is characterized in that described to contain carboxylic
The chain extender of base is 2,2- dihydromethyl propionic acid.
6. the organic-silicon-modified water according to claim 1 for synthetic leather rubs auxiliary agent, which is characterized in that the neutralizer
For triethylamine or ammonium hydroxide.
7. the organic-silicon-modified water according to claim 1 for synthetic leather rubs auxiliary agent, which is characterized in that the amine expands
Chain agent is ethylenediamine.
8. the organic-silicon-modified water according to claim 1 for synthetic leather rubs auxiliary agent, which is characterized in that the catalyst
For organic bismuth catalyst.
It is used to prepare the organic-silicon-modified water according to claim 1 to 8 for synthetic leather 9. a kind of and rubs auxiliary agent
Method, which is characterized in that comprise the steps of
(1) reaction raw materials are weighed in proportion；
(2) polymerization reaction: weighed epoxy silicon oil, isocyanates, catalyst are placed in reaction vessel, in the first predetermined temperature
Reaction 1-2 hours；
(3) chain extension is handled: weighed polyether-containing aminopolysiloxane being added into reaction vessel, water-miscible organic solvent, contains carboxylic
The chain extender of base reacts qualified to measured NCO% in the second predetermined temperature；
(4) decentralized processing: adding neutralizer into reaction vessel, reacts 5-15 minutes, in the case where high speed dispersion thereto
Deionized water emulsification is imported, is added later through water-reducible amine chain extender, is reacted 10-30 minutes, obtains the aqueous poly- of modification
Urethane resin.
10. according to the method described in claim 9, it is characterized in that, first predetermined temperature be 60-70 DEG C, described second
Predetermined temperature is 70-80 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116355389A (en) * | 2023-04-21 | 2023-06-30 | 广东安拓普聚合物科技有限公司 | Composite material for cold water pipe of charging pile of new energy automobile |
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| CN116355389A (en) * | 2023-04-21 | 2023-06-30 | 广东安拓普聚合物科技有限公司 | Composite material for cold water pipe of charging pile of new energy automobile |
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Application publication date: 20191126 |