CN108892779A - A kind of preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate - Google Patents
A kind of preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate Download PDFInfo
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- CN108892779A CN108892779A CN201810627351.3A CN201810627351A CN108892779A CN 108892779 A CN108892779 A CN 108892779A CN 201810627351 A CN201810627351 A CN 201810627351A CN 108892779 A CN108892779 A CN 108892779A
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- organosiliconcopolymere
- blocked isocyanate
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- diisocyanate
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
-
- 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
- C08G18/48—Polyethers
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
-
- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
Abstract
The present invention provides a kind of preparation methods of the modified quaternized Organosiliconcopolymere of blocked isocyanate.Preparation method is to react epoxy terminated polysiloxanes with the compound containing tertiary amine group, then diisocyanate is added, polyether polyol or polyetheramine carry out step-reaction polymerization, are eventually adding sealer sealing end, obtain the polyurethane-modified Organosiliconcopolymere containing quaternary ammonium salt.The modified quaternized Organosiliconcopolymere of blocked isocyanate of the invention, compared to Siloxane-Oxyalkylene Copolymers in original technology, position is held to have closed isocyanate groups, the closing of isocyanates can be kept at room temperature, and under suitable condition, closed isocyanate groups can unseal, charge effect or cross-linking reaction occurs with the group on fabric, it can effectively solve shelf stability and fabric the hydrophilic washing fastness of isocyanate group modified organic silicon, technique is relatively simple, and operating condition is easily controllable.
Description
Technical field
The invention belongs to the fields of textile finish, and in particular to a kind of blocked isocyanate modification is quaternized organic
The preparation method of siliceous copolymer.
Background technique
Polyurethane-modified organosilicon can overcome the macromolecule of single variety in conjunction with the advantages of polyurethane and organosilicon
The shortcomings that object, the excellent properties with polyurethane while retaining silicone softening agent improved flexibility.Patent
CN20160826047.2 discloses a kind of preparation method of polysiloxane-polyurethane copolymer fabric softener that feel is excellent.Though
The flexibility of amido silicon oil, resilience are so remained, and there is certain hydrophily, vividness and whiteness, but its is smooth
It still can not meet the demand in market with hydrophily.Patent CN201410315223.7 introduces quaternized knot in silicone segments
Structure not only greatly improves the hydrophily of copolymer, but also can assign soft fabric, fine and smooth cool silk sliding function, can be effective
Improve existing amino silicone class to arrange.
Organosilicon is the surface for being covered on fiber as softening agent, and water-soluble organic silicon is again soluble easily in water, so water-soluble
Organosilicon as softening agent there is also durability, water-wash resistance is poor the deficiencies of place, do not adapt to more high-grade needs.Separately
Outside, the modified polyether silicones of diisocyanate are very sensitive to moisture there is free isocyanate groups reactivity is big
The problems such as, seriously affect its usability and Storage.The present invention provides a kind of case type isocyanate-modified quaternized organic
Siliceous copolymer can keep the closing of isocyanates at room temperature, and under suitable condition, and closed isocyanate groups can be with
Deblocking occurs charge effect or cross-linking reaction with the group on fabric, can effectively solve isocyanate group modified organic silicon
Shelf stability and fabric hydrophilic washing fastness.
Summary of the invention
The primary purpose of the present invention is that providing a kind of system of modified quaternized Organosiliconcopolymere of blocked isocyanate
Preparation Method further increases the washable enduring quality of polyurethane-modified Organosiliconcopolymere, with overcome the deficiencies in the prior art.
The purpose of the invention is achieved by the following technical solution：
Firstly, epoxy terminated polysiloxanes is reacted with the compound containing tertiary amine group, diisocyanate is then added
Ester, polyether polyol or polyetheramine carry out step-reaction polymerization, are eventually adding sealer sealing end, obtain the poly- ammonia containing quaternary ammonium salt
Ester modified Organosiliconcopolymere.
The preparation method of the polyurethane-modified Organosiliconcopolymere containing quaternary ammonium salt, specific step is as follows：
1) blender is being housed, thermometer, reflux condensing tube and nitrogen are blown into four mouthfuls of reaction units of pipe and are added 100
The epoxy terminated polysiloxanes of part adds containing tertiary amine compounds and neutralizes agent composition, is stirred to react 3- in 60-100 DEG C
8 hours, obtain the polysiloxanes containing quaternary ammonium salt；
Wherein,
In step (1), the epoxy terminated polysiloxanes has the general structure as shown in following formula (I)：
Wherein, in formula (I), n be 25~400 natural number；
In step (1), described has general structure shown in following (II) containing tertiary amine compounds：
Wherein, in formula (II), m be 1~20 natural number；R1For alkyl chain, carbon number is 1~3；R2For CH3, or-NH2,
Or-OH；R3For alkyl chain or branched alkyl chain, carbon number is 1~20, and dosage is the 0.65-12% of epoxy silicon oil molal quantity.
In step (1), the neutralizer is selected from one of formic acid, acetic acid, propionic acid, lauric acid, is three-level amine compounds
The 90%-110% of object molal quantity.
2) the addition 1-50 parts of diisocyanate, 30-100 parts of solvents in quaternary ammonium salt polysiloxanes among the above, 3-30 parts
Polyether Glycols or polyetheramine and catalyst are stirred to react 5-12 hours at 25-100 DEG C, are analyzed with di-n-butylamine method residual
Stay NCO content, wait after reaching calculated value, 1-10 parts of sealers are then added, the reaction was continued 1 hour until NCO fully reacting,
It is down to room temperature, obtains the modified quaternized Organosiliconcopolymere of blocked isocyanate；
Wherein,
In step (2), the diisocyanate is selected from isofoer diisocyanate (IPDI), hexamethylene diisocyanate
(HDI), ditolyl methane diisocyanate (MDI), sub- xylylene diisocyanate (XDI) or toluene di-isocyanate(TDI)
Or no less than two kinds of combination one of (TDI)；
In step (2), the solvent be acetone, methyl butyl ketone, butanone, glycol dimethyl ether, diethylene glycol dimethyl ether,
One of butyl cellosolve, dibutyl ethylene glycol ether, Propylene Glycol Dimethyl Ether, dimethyl ether；
In step (2), the catalyst is one in organotin catalysts, organozinc catalyst and organic bismuth catalyst
Kind, wherein preferred organotin catalysts are dibutyltin dilaurate, dosage is quaternary ammonium salt polysiloxanes, diisocyanate
The 0.1-0.5% of ester and polyethers gross mass；
In step (2), the polyether polyol is polyethylene glycol, polypropylene glycol or both copolymerization and poly- tetrahydro furan
It mutters one of ether glycol or no less than two kinds of combination, molecular weight 300-6000；
In step (2), the polyetheramine is the polyethers of primary amine sealing end, has general structure shown in following (III)：
Wherein, in formula (III), x+y+z be 1~70 natural number.
In step (2), the sealer is ethyl alcohol, phenol, caprolactam, diethyl malonate, acetoacetate second
Ester, one or more of acetoxime, methyl ethyl ketoxime, acetylacetone,2,4-pentanedione, sodium hydrogensulfite.
Compared with prior art, the present invention having the following advantages that and effect：Polyurethane-modified organosilicon copolymerization of the invention
Contain quaternized structure in owner's chain, improves the hydrophily of copolymer, and soft and smooth and endurance quality can be effectively improved.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
The end 100g epoxy silicon oil (molecular weight 8000, m ≈ 105) is added to four equipped with thermometer and reflux condensing tube
In mouth flask, under agitation, 5.3gN, N- dimethyl lauryl amine and lauric acid 5g is added, it is small to be stirred to react 5 in 80 DEG C
When, obtain the polysiloxanes containing quaternary ammonium salt；Then, isophorone diisocyanate 8.5g, solvent dimethyl ether is added
30g is added 15g polyetheramine ED900 (molecular weight 900, x+z=6, y=12.5), catalyst dibutyltin dilaurate
0.1g is stirred to react 6 hours at 60 DEG C, is analyzed residual NCO content with di-n-butylamine method, is waited after reaching calculated value, add envelope
Agent diacetylmonoxime 3g is closed, is stirred to react at 60 DEG C 1 hour, it is total to obtain the modified quaternized organosilicon of diacetylmonoxime blocked isocyanate
Polymers.
Embodiment 2
The end 100g epoxy silicon oil (molecular weight 2000, m ≈ 25) is added to four mouthfuls equipped with thermometer and reflux condensing tube
In flask, under agitation, 11.7g N, N- diethyl ethylenediamine and propionic acid 15g is added, is stirred to react in 60 DEG C 3 hours,
Obtain the polysiloxanes containing quaternary ammonium salt；Then, methyl diphenylene diisocyanate 35g, solvent butanone 30g is added, 16g is added
Polyetheramine ED400 (molecular weight 900, x+z=6, y=0), catalyst dibutyltin dilaurate 0.2g are anti-in 25 DEG C of stirrings
It answers 5 hours, analyzes residual NCO content with di-n-butylamine method, wait after reaching calculated value, add sealer diacetylmonoxime 10g,
25 DEG C are stirred to react 1 hour, obtain the modified quaternized Organosiliconcopolymere of diacetylmonoxime blocked isocyanate.
Embodiment 3
The end 100g epoxy silicon oil (molecular weight 12000, m ≈ 160) is added to four equipped with thermometer and reflux condensing tube
In mouth flask, under agitation, 1.5g N, N- dimethylethanolamine and acetic acid 1.2g is added, it is small to be stirred to react 6 in 80 DEG C
When, obtain the polysiloxanes containing quaternary ammonium salt；Then, six hexyl diisocyanate 6.05g, solvent dimethyl ether is added
80g is added 7g hydroxy polyethers PEG-PPG100 (molecular weight 1000, a=12, b=8), catalyst dibutyltin dilaurate
0.3g is stirred to react 8 hours at 80 DEG C, is analyzed residual NCO content with di-n-butylamine method, is waited after reaching calculated value, add envelope
Agent acetoxime 3.2g is closed, is stirred to react at 80 DEG C 1 hour, the modified quaternized organosilicon of acetoxime blocked isocyanate is obtained
Copolymer.
Embodiment 4
The end 100g epoxy silicon oil (molecular weight 15000, m ≈ 200) is added to four equipped with thermometer and reflux condensing tube
In mouth flask, under agitation, 1.0g N, N- dimethyl amine and acetic acid 1.0g is added, is stirred to react in 90 DEG C 3 hours,
Obtain the polysiloxanes containing quaternary ammonium salt；Then, toluene di-isocyanate(TDI) 3.0g is added, solvent dibutyl ethylene glycol ether 80g adds
Enter 5.0g polyetheramine ED900 (molecular weight 900, x+z=6, y=12.5), catalyst dibutyltin dilaurate 0.3g,
100 DEG C are stirred to react 6 hours, analyze residual NCO content with di-n-butylamine method, wait after reaching calculated value, add sealer second
Ethyl acetoacetic acid ethyl ester 3.0g is stirred to react 1 hour at 80 DEG C, obtains the modified quaternized Organosiliconcopolymere of blocked isocyanate.
Embodiment 5
The end 100g epoxy silicon oil (molecular weight 30000, m ≈ 400) is added to four equipped with thermometer and reflux condensing tube
In mouth flask, under agitation, 0.65g N, N- dimethylethanolamine and acetic acid 0.5g is added, is stirred to react 8 in 100 DEG C
Hour, obtain the polysiloxanes containing quaternary ammonium salt；Then, toluene di-isocyanate(TDI) 2.2g, solvent acetone 100g is added, is added
5.0g hydroxy polyethers PEG-PPG100 (molecular weight 1000, a=12, b=8), catalyst dibutyltin dilaurate 0.5g,
It is stirred to react at 80 DEG C 12 hours, analyzes residual NCO content with di-n-butylamine method, wait after reaching calculated value, add sealer
Ethyl acetoacetate 2.0g is stirred to react 1 hour at 80 DEG C, obtains the modified quaternized organosilicon copolymerization of blocked isocyanate
Object.
Comparative example
The end 100g epoxy silicon oil (molecular weight 8000, m ≈ 105) is added to four equipped with thermometer and reflux condensing tube
In mouth flask, under agitation, 5.3g N, N- dimethyl lauryl amine and lauric acid 5g is added, it is small to be stirred to react 5 in 80 DEG C
When, obtain the polysiloxanes containing quaternary ammonium salt；Then, isophorone diisocyanate 8.5g, solvent dimethyl ether is added
30g is added 25g polyetheramine ED900 (molecular weight 900, x+z=6, y=12.5), catalyst dibutyltin dilaurate
0.1g is stirred to react 6 hours at 60 DEG C, is analyzed residual NCO content with di-n-butylamine method and is obtained non-envelope until NCO has reacted
The isocyanate-modified quaternized Organosiliconcopolymere of closed form.
Application Example
Contrast standard：The above silicone oil is configured to 20% aqueous solution, comparing cloth specimen is that pure white is knitted cotton, and dosage is
10g/L, an immersing and rolling are dried 90 seconds in 170 DEG C of setting.
Evaluation method：The feel mainly integrated survey in terms of flexibility and flatness, is touched by several experts are blind, and 5 grades are preferably,
1 grade worst.
The hydrophily of fabric passes through the timing definition that one drop water of measurement is absorbed by fabric completely in seconds.
Comparison result is as follows：
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate, it is characterised in that：By end ring oxygen
The polysiloxanes of base is reacted with the compound containing tertiary amine group, and diisocyanate, polyether polyol or polyethers is then added
Amine carries out step-reaction polymerization, is eventually adding sealer sealing end, obtains the polyurethane-modified Organosiliconcopolymere containing quaternary ammonium salt.
2. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 1, feature
It is to include the following steps：
1) blender, thermometer are being housed, reflux condensing tube and nitrogen are blown into 100 parts of ends of addition in four mouthfuls of reaction units of pipe
The polysiloxanes of epoxy group adds containing tertiary amine compounds and neutralizes agent composition, it is small to be stirred to react 3-8 in 60-100 DEG C
When, obtain the polysiloxanes containing quaternary ammonium salt；
2) 1-50 parts of diisocyanate, 30-100 parts of solvents, 3-30 parts of polyethers are added in quaternary ammonium salt polysiloxanes among the above
Dihydric alcohol or polyetheramine and catalyst are stirred to react 5-12 hours at 25-100 DEG C, analyze residual NCO with di-n-butylamine method
Content waits after reaching calculated value, then be added 1-10 parts of sealers, the reaction was continued 1 hour until NCO fully reacting, be down to room
Temperature obtains the modified quaternized Organosiliconcopolymere of blocked isocyanate.
3. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：In step 1), the epoxy terminated polysiloxanes has the following structure general formula：
Wherein, the natural number that n is 25~400.
4. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：It is described to have the following structure general formula containing tertiary amine compounds in step 1)：
Wherein, the natural number that m is 1~20；R1For alkyl chain, carbon number is 1~3；R2For CH3, or-NH2, or -0H；R3For alkyl
Chain or branched alkyl chain, carbon number are 1~20, and dosage is the 0.65-12% of epoxy silicon oil molal quantity.
5. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：In step 1), the neutralizer is selected from one of formic acid, acetic acid, propionic acid, lauric acid, is tertiary amine compounds mole
Several 90%-110%.
6. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：In step 2), the diisocyanate is selected from isofoer diisocyanate (IPDI), hexamethylene diisocyanate (HDI), two
One in toluene methane diisocyanate (MDI), sub- xylylene diisocyanate (XDI) or toluene di-isocyanate(TDI) (TDI)
Kind or no less than two kinds of combination.
7. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：In step 2), the solvent is acetone, methyl butyl ketone, butanone, glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol two
One of butyl ether, dibutyl ethylene glycol ether, Propylene Glycol Dimethyl Ether, dimethyl ether.
8. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：In step 2), the catalyst is one of organotin catalysts, organozinc catalyst and organic bismuth catalyst,
In preferred organotin catalysts be dibutyltin dilaurate, dosage is quaternary ammonium salt polysiloxanes, diisocyanate and poly-
The 0.1-0.5% of ether gross mass；The polyether polyol is polyethylene glycol, polypropylene glycol or both copolymerization and poly- tetrahydro furan
It mutters one of ether glycol or no less than two kinds of combination, molecular weight 300-6000.
9. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：In step 2), the polyetheramine is the polyethers of primary amine sealing end, has the following structure general formula：
Wherein, the natural number that x+y+z is 1~70.
10. the preparation method of the modified quaternized Organosiliconcopolymere of blocked isocyanate according to claim 2, feature
It is：In step 2), the sealer is ethyl alcohol, phenol, caprolactam, diethyl malonate, ethyl acetoacetate, acetone
One or more of oxime, methyl ethyl ketoxime, acetylacetone,2,4-pentanedione, sodium hydrogensulfite.
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| CN109943077A (en) * | 2019-03-13 | 2019-06-28 | 长沙集智创新工业设计有限公司 | A kind of preparation process of modified silica-gel sealing ring |
| CN112726211A (en) * | 2021-01-13 | 2021-04-30 | 日华化学（中国）有限公司 | Preparation method of polyurethane modified organic silicon softening agent |
| CN114775291A (en) * | 2022-05-16 | 2022-07-22 | 杭州美高华颐化工有限公司 | Preparation method of novel quaternized modified block silicone oil |
| CN115787301A (en) * | 2022-11-18 | 2023-03-14 | 杭州传化精细化工有限公司 | Polyurethane modified organic silicon softener and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943077A (en) * | 2019-03-13 | 2019-06-28 | 长沙集智创新工业设计有限公司 | A kind of preparation process of modified silica-gel sealing ring |
| CN112726211A (en) * | 2021-01-13 | 2021-04-30 | 日华化学（中国）有限公司 | Preparation method of polyurethane modified organic silicon softening agent |
| CN114775291A (en) * | 2022-05-16 | 2022-07-22 | 杭州美高华颐化工有限公司 | Preparation method of novel quaternized modified block silicone oil |
| CN114775291B (en) * | 2022-05-16 | 2023-06-27 | 杭州美高华颐化工有限公司 | Preparation method of novel quaternized modified block silicone oil |
| CN115787301A (en) * | 2022-11-18 | 2023-03-14 | 杭州传化精细化工有限公司 | Polyurethane modified organic silicon softener and preparation method and application thereof |
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Application publication date: 20181127 |