CN115975205A - Preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion - Google Patents
Preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion Download PDFInfo
- Publication number
- CN115975205A CN115975205A CN202310044130.4A CN202310044130A CN115975205A CN 115975205 A CN115975205 A CN 115975205A CN 202310044130 A CN202310044130 A CN 202310044130A CN 115975205 A CN115975205 A CN 115975205A
- Authority
- CN
- China
- Prior art keywords
- amino
- silicone oil
- emulsifying
- self
- polyether
- 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.)
- Granted
Links
- 229920013822 aminosilicone Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000839 emulsion Substances 0.000 title claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 67
- 229920000570 polyether Polymers 0.000 claims abstract description 67
- 229920001400 block copolymer Polymers 0.000 claims abstract description 30
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 21
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 15
- -1 polysiloxane Polymers 0.000 claims description 42
- 229920001296 polysiloxane Polymers 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000007142 ring opening reaction Methods 0.000 claims description 11
- 230000002140 halogenating effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 9
- 101150065749 Churc1 gene Proteins 0.000 claims description 9
- 102100038239 Protein Churchill Human genes 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 24
- 239000004744 fabric Substances 0.000 abstract description 20
- 239000000675 fabric finishing Substances 0.000 abstract description 4
- 238000009962 finishing (textile) Methods 0.000 abstract description 4
- 230000003068 static effect Effects 0.000 abstract 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 23
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 125000001302 tertiary amino group Chemical group 0.000 description 7
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 4
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 4
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 4
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 4
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 3
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- YJRGMUWRPCPLNH-UHFFFAOYSA-N butyl 2-chloroacetate Chemical compound CCCCOC(=O)CCl YJRGMUWRPCPLNH-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 101100394003 Butyrivibrio fibrisolvens end1 gene Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QMCVOSQFZZCSLN-QXMHVHEDSA-N dihexyl (z)-but-2-enedioate Chemical compound CCCCCCOC(=O)\C=C/C(=O)OCCCCCC QMCVOSQFZZCSLN-QXMHVHEDSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- BNWCETAHAJSBFG-UHFFFAOYSA-N tert-butyl 2-bromoacetate Chemical compound CC(C)(C)OC(=O)CBr BNWCETAHAJSBFG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The application relates to the technical field of fabric finishing agents, and particularly provides a preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion. The preparation method of the self-emulsifying amino silicone oil is obtained by reacting double-amino-terminated polyether-polysiloxane-polyether block copolymer with dialkyl maleate. Preferably, quaternization can also be carried out. The amino silicone oil emulsion obtained from the self-emulsifying amino silicone oil can be used as a fabric finishing agent to endow the fabric with the properties of low yellowing, static resistance, softness and the like.
Description
Technical Field
The application relates to the technical field of fabric finishing agents, in particular to a preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion.
Background
The amino silicone oil emulsion is an excellent fabric finishing agent and can endow fabrics with smooth and fluffy handfeel. Conventional amino silicone emulsions are primary amino, but tend to cause yellowing of fabrics. Changing the primary amino group in the amino silicone oil emulsion to a secondary amino group can reduce yellowing of the fabric.
Disclosure of Invention
The inventor thinks that the prior secondary amino-type amino silicone oil emulsion can further reduce the yellowing of fabrics, and through a great deal of analysis, experiments and researches, the inventor finds an amino silicone oil emulsion finishing agent capable of obviously reducing the yellowing of fabrics, and then proposes the application.
The technical scheme is as follows:
a preparation method of self-emulsifying amino silicone oil is obtained by reacting double-amino-terminated polyether-polysiloxane-polyether block copolymer with dialkyl maleate;
the dialkyl maleate has a structure shown in a formula (1),
preferably, the amino-terminated polyether-polysiloxane-polyether block copolymer is obtained by reacting an amino-terminated polyether with an epoxy-terminated polysiloxane, or by reacting an amino-terminated polyether with an anhydride-terminated polysiloxane.
Preferably, the molar ratio of the double amino-terminated polyether-polysiloxane-polyether block copolymer to the dialkyl maleate is from 1.
Preferably, said R is 1 Selected from C4-C12 alkyl.
Preferably, the reaction of the double-amino-terminated polyether-polysiloxane-polyether block copolymer and dialkyl maleate further comprises the following steps: carrying out quaternization reaction.
More preferably, the quaternization reaction is performed by adding epichlorohydrin.
More preferably, the quaternization reaction is carried out by adding an epoxy group-containing compound to carry out a ring-opening reaction and then adding a halogenating agent to carry out a reaction.
Further preferably, the epoxy group-containing compound is selected from the group consisting of C1-C14 alkyl glycidyl ethers and compounds of the general formula R 2 O(CH 2 CH 2 O) a (CH 2 CHCH 3 O) b CH 2 (CHCH 2 O) one or more of epoxy polyether, wherein R 2 Selected from H, C1-C20 alkyl or C1-C20 substituted alkyl, a =1-100, b =0-100.
Further preferably, the halogenating agent is one or more selected from chloro-organic compounds, bromo-organic compounds and iodo-organic compounds.
An amino silicone oil emulsion obtained from the self-emulsifying amino silicone oil prepared by the preparation method according to any one of the above embodiments.
In summary, the present application has the following beneficial effects:
1. the self-emulsifying amino silicone oil is linear chain amino silicone oil, the effect is good, a secondary amino group is formed after the primary amino group of the end group reacts with dialkyl maleate, and the secondary amino group has low activity and is not easy to yellow due to the surrounding and steric hindrance effect of an aspartic ester structure and the electron withdrawing effect of the aspartic ester.
2. It has further been found in the present application that the alkyl group in the dialkyl maleate is a C4-C12 alkyl group, and that the secondary amino group in the self-emulsifying amino silicone oil of the present application is less reactive, probably due to steric shielding and hydrophobic effects of the C4-C12 alkyl group.
3. The self-emulsifying amino silicone oil can be further subjected to tertiary amination and/or quaternization, and can improve the yellowing resistance of the amino silicone oil emulsion.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
On one hand, the application provides a preparation method of self-emulsifying amino silicone oil, which is obtained by reacting double-end amino-terminated polyether-polysiloxane-polyether block copolymer with dialkyl maleate;
the dialkyl maleate has a structure shown in a formula (1),
in the application, the amino group of the amino group-terminated polyether-polysiloxane-polyether block copolymer is primary amino group, and the reaction of the amino group-terminated polyether-polysiloxane-polyether block copolymer and dialkyl maleate is a Michael addition reaction of amino group and carbon-carbon unsaturated double bond, wherein the primary amino group is converted into secondary amino group, and the structure formed by the reaction of the primary amino group and dialkyl maleate is shown in the following formula (2).
The secondary amino group has a lower activity and is less likely to yellow.
In a preferred embodiment of the present application, the amino-terminated polyether-polysiloxane-polyether block copolymer is obtained by reacting an amino-terminated polyether with an epoxy-terminated polysiloxane, or by reacting an amino-terminated polyether with an anhydride-terminated polysiloxane.
In the present application, the amine terminated polyether is a hydrophilic polyether, for example, an amine terminated polyether having a chemical formula of NH 2 CH 2 CH 2 O(CH 2 CH 2 O) m (CH 2 CHCH 3 O) n CH 2 CH 2 NH 2 Wherein m =3-200, n =0-200, m ≧ n. The general chemical structure formula of the epoxy terminated polysiloxane is R 3 Si(CH 3 ) 2 O(SiCH 3 R 4 O) x Si(CH 3 ) 2 R 3 Wherein R is 3 Is represented by (OCH) 2 CH)OCH 2 CH 2 CH 2 -,R 4 Selected from methyl, phenyl, 3-trifluoropropyl, 3-chloropropyl, etc., and x =10-200. The bis-epoxy polysiloxanes of the present application can be obtained by hydrosilylation reaction of the corresponding hydrogen-terminated polysiloxane with allyl glycidyl ether, which is well known to the person skilled in the art.
The reactivity of the amino and epoxy groups is higher. According to the preparation method, hydrophilic double-end amino polyether and double-end epoxy polysiloxane are subjected to ring-opening reaction to obtain the linear chain amino silicone oil. Specifically, the molar ratio of the amino-terminated polyether to the epoxy-terminated polysiloxane may be 1.3 to 2.2, or, further, may be 1.8 to 2.1, and the molar ratio of the amino-terminated polyether to the epoxy-terminated polysiloxane may be, for example, 1.8.
In the present application, the amino-terminated polyether-polysiloxane-polyether block copolymer can also be obtained by reacting amino-terminated polyether with anhydride-terminated polysiloxane, wherein the anhydride-terminated polysiloxane means that the two terminal groups of the polysiloxane are anhydride groups. The amino group can undergo a ring-opening reaction with an acid anhydride to form an amide and a carboxyl group. Specifically, the molar ratio of the amino-terminated polyether to the anhydride-terminated polysiloxane can be 1.8 to 2.2, and for example, the molar ratio can be 1.8.
In a preferred embodiment herein, the molar ratio of amino-terminated double-ended polyether-polysiloxane-polyether block copolymer to dialkyl maleate is from 1. More preferably, the molar ratio of the amino-terminated double-ended polyether-polysiloxane-polyether block copolymer to the dialkyl maleate is from 1.
By the above embodiment, both terminal amino groups are converted into secondary amino groups, and the excess dialkyl maleate can be removed by distillation or distillation under reduced pressure, or the like.
In a preferred embodiment of the present application, R 1 Selected from C4-C12 alkyl. R 1 When the alkyl is C4-C12 alkyl, the C4-C12 has certain space shielding effect and hydrophobic effect, and the yellowing resistance of secondary amine groups is further improved. But R is 1 The carbon chain of (2) is not suitable to be overlong, and the overlong carbon chain can cause the hydrophilicity of the amino silicone oil to be reduced due to the stronger hydrophobic effect, so that the self-emulsification cannot be realized.
In a preferred embodiment of the present application, the reaction of the amino terminated double-ended polyether-polysiloxane-polyether block copolymer with dialkyl maleate further comprises the following steps: carrying out quaternization reaction. When the amino-terminated polyether-polysiloxane-polyether block copolymer is obtained by reacting an amino-terminated polyether with an epoxy-terminated polysiloxane, an epoxy group and an amino group undergo a ring-opening reaction to form a secondary amino structure (secondary amino 1), the reactivity of the secondary amino 1 is higher than that of a secondary amino (secondary amino 2) obtained by reacting a primary amino group with a dialkyl maleate, and quaternization is easier to perform, but the yellowing resistance is better due to the steric shielding effect because the secondary amino 1 is inside a linear molecular structure. The quaternization of the secondary amino 1 can improve the hydrophilicity of the amino silicone oil, better realize self-emulsification, and provide sterilization and antibacterial effects, better flexibility and antistatic performance for fabrics and the like.
In a more preferred embodiment of the present application, the quaternization reaction is performed by adding epichlorohydrin. The secondary amino 1 can directly react with epichlorohydrin to obtain a quaternary ammonium salt structure, and specifically, the molar ratio of the self-emulsifying amino silicone oil to the epichlorohydrin is 1.5-5. Furthermore, the reaction condition can be an absolute ethyl alcohol reaction system, the reaction temperature is 50-80 ℃, the reaction time is 6-8 hours, and a small amount of quaternary ammonium salt (such as tetramethyl ammonium hydroxide) can also be added as an accelerant.
In a more preferred embodiment of the present application, the quaternization is carried out by adding an epoxy group-containing compound to carry out a ring-opening reaction and then adding a halogenating agent to carry out the reaction. The secondary amino group 1 can be subjected to a ring-opening reaction with an epoxy group-containing compound to form a tertiary amine group, and the tertiary amine group is subjected to a quaternization reaction. Specifically, when the ring-opening reaction is carried out on the self-emulsifying amino silicone oil and the epoxy group compound, the molar ratio of the self-emulsifying amino silicone oil to the epoxy group compound is 1.3-5, the reaction temperature can be 15-60 ℃, and the reaction time can be 1-5 hours. And carrying out quaternization reaction with a halogenating agent, wherein the molar ratio of the self-emulsifying amino silicone oil to the halogenating agent can be 1 to 0.3-4, the reaction temperature can be 50-80 ℃, and the reaction time can be 10-40 hours.
The ring-opening reaction of the secondary amino group 1 and the epoxy group-containing compound can partially or completely convert the secondary amino group 1 into a tertiary amine group, and the yellowing resistance of the tertiary amine group is better than that of the secondary amino group 1. And then converting part or all of the tertiary amine groups into quaternary ammonium salt by using a halogenating reagent.
In a further preferred embodiment of the present application, the epoxy group-containing compound is selected from C1-C14 alkyl glycidyl ethers and compounds of the general formula R 2 O(CH 2 CH 2 O) a (CH 2 CHCH 3 O) b CH 2 (CHCH 2 O) one or more of epoxy polyether, wherein R 2 Selected from H, C1-C20 alkyl or C1-C20 substituted alkyl, a =1-100, b =0-100. The C1-C14 alkyl glycidyl ether can perform ring-opening reaction with the secondary amino 1 to form a tertiary amine group, and further preferably, the alkyl glycidyl ether is C1-C4 alkyl glycidyl ether, so that the influence on the hydrophilicity of the self-emulsifying amino silicone oil can be avoided. The epoxy polyether can also perform a ring-opening reaction with the secondary amino 1 to form a tertiary amine group, and further preferably, the epoxy polyether is hydrophilic epoxy polyether, so that the hydrophilicity of the self-emulsifying amino silicone oil can be improved, and the self-emulsifying property is improved.
In a further preferred embodiment of the present application, the halogenating agent is selected from one or more of chlorinated organic compounds, brominated organic compounds and iodinated organic compounds. Examples of the halogenating agent include chlorooctadecane, chlorooctane, chloromethane, bromooctane, chlorohexadecyl, chlorododecane, ethyl chloroacetate, ethyl bromoacetate, bromooctadecane, butyl chloroacetate, t-butyl bromoacetate, epichlorohydrin and the like.
In another aspect, the present application provides an amino silicone oil emulsion obtained from the self-emulsifying amino silicone oil prepared by the preparation method according to any of the above embodiments.
The amino silicone oil emulsion of the present application can be prepared as follows: under the condition of vigorous stirring, a certain amount of water is added into the self-emulsifying amino silicone oil, and the pH value of the system is adjusted to 5.5-6 after stirring and dispersing. The aminosilicone emulsion of the present application is a transparent to translucent blue light emitting microemulsion or a slightly opaque blue light emitting microemulsion, and the solid content may be 5-50wt%, or further, the solid content of the aminosilicone emulsion may be 10-40wt%.
The technical scheme of the application will be described in detail by combining examples, comparative examples and experimental data.
Unless otherwise specified, the parts in each of the following examples and comparative examples are parts by weight.
Description of the raw materials
Double end1, amino polyether: NH 2 CH 2 CH 2 O(EO) 32.6 (PO) 10.4 CH 2 CH 2 NH 2 EO represents CH 2 CH 2 O, PO represent CH 2 CHCH 3 O;
Amino-terminated polyether 2: NH (NH) 2 CH 2 CH 2 O(EO) 15.7 CH 2 CH 2 NH 2 ;
Epoxy-terminated polysiloxane 1: r is 3 Si(CH 3 ) 2 O(SiCH 3 CH 3 O) 45.9 Si(CH 3 ) 2 R 3 ,R 3 Is represented by (OCH) 2 CH)OCH 2 CH 2 CH 2 -;
Epoxy-terminated polysiloxane 2: r is 3 Si(CH 3 ) 2 O(SiCH 3 CH 3 O) 70.4 Si(CH 3 ) 2 R 3 ,R 3 Is represented by (OCH) 2 CH)OCH 2 CH 2 CH 2 -;
Preparation example 1
Adding amino-terminated polyether 1 and epoxy-terminated polysiloxane 1 into a reaction vessel according to the mol ratio of 1.9, adding butyl acetate 4 times the weight of the amino-terminated polyether 1 and the epoxy-terminated polysiloxane 1, stirring and reacting at 15 ℃ for 2 hours, heating to 50 ℃, continuing to react for 2 hours, and removing butyl acetate to obtain amino-terminated polyether-polysiloxane-polyether block copolymer, which is marked as P-1.
Preparation example 2
Adding amino-terminated polyether 1 and epoxy-terminated polysiloxane 2 into a reaction vessel according to the mol ratio of 2 to 1, adding butyl acetate which is 5 times of the weight of the amino-terminated polyether 1 and the epoxy-terminated polysiloxane 2, stirring and reacting for 2 hours at 15 ℃, heating to 50 ℃, continuing to react for 2.5 hours, removing the butyl acetate, and obtaining the amino-terminated polyether-polysiloxane-polyether block copolymer, which is marked as P-2.
Preparation example 3
Adding amino-terminated polyether 2 and epoxy-terminated polysiloxane 1 into a reaction vessel according to a molar ratio of 1.95, adding tetrahydrofuran which is 4 times of the weight of the amino-terminated polyether 2 and the epoxy-terminated polysiloxane 1, stirring and reacting at 15 ℃ for 2 hours, heating to 50 ℃ and continuing to react for 2 hours, and removing the tetrahydrofuran to obtain an amino-terminated polyether-polysiloxane-polyether block copolymer, which is marked as P-3.
Preparation example 4
Adding amino-terminated polyether 2 and epoxy-terminated polysiloxane 2 into a reaction vessel according to the molar ratio of 2 to 1, adding tetrahydrofuran which is 4 times the weight of the amino-terminated polyether 2 and the epoxy-terminated polysiloxane 2, stirring and reacting for 2 hours at 15 ℃, heating to 50 ℃, continuing to react for 2.5 hours, removing the tetrahydrofuran, and obtaining the amino-terminated polyether-polysiloxane-polyether block copolymer, which is marked as P-4.
Example 1
Mixing the double-end amino-terminated polyether-polysiloxane-polyether block copolymer P-1 of preparation example 1 and dimethyl maleate according to a molar ratio of 1:2.02, adding sodium methoxide with the total weight of P-1 and dimethyl maleate being 0.03%, heating to 90 ℃ under the protection of nitrogen, reacting for 36h, and removing unreacted dimethyl maleate under reduced pressure to obtain self-emulsifying amino silicone oil, which is marked as S-1.
Example 2
The dimethyl maleate in example 1 was replaced by an equimolar portion of dihexyl maleate and the rest of the procedure was kept unchanged, obtaining a self-emulsifying amino silicone oil, noted S-2.
Example 3
The amino-terminated polyether-polysiloxane-polyether block copolymer P-2 of preparation example 2 and dioctyl maleate were mixed in a molar ratio of 1:2, sodium methoxide, 0.03% of the total weight of P-2 and dioctyl maleate, was added, the mixture was heated to 90 ℃ under nitrogen protection to react for 30 hours, and unreacted dioctyl maleate was removed under reduced pressure to obtain self-emulsifying amino silicone oil, which was designated as S-3.
Example 4
The double-end amino-terminated polyether-polysiloxane-polyether block copolymer P-3 of preparation example 3 and dibutyl maleate were mixed according to a molar ratio of 1:2.05, sodium methoxide, which was 0.03% of the total weight of P-3 and dibutyl maleate, was added, the mixture was heated to 90 ℃ under nitrogen protection to react for 40 hours, and unreacted dibutyl maleate was removed under reduced pressure to obtain self-emulsifying amino silicone oil, which was designated as S-4.
Example 5
Mixing the double-end amino-terminated polyether-polysiloxane-polyether block copolymer P-4 of preparation example 4 and diethyl maleate according to a molar ratio of 1:2.05, adding sodium methoxide with the total weight of P-4 and diethyl maleate being 0.03%, heating to 90 ℃ under the protection of nitrogen, reacting for 40h, and removing unreacted diethyl maleate under reduced pressure to obtain self-emulsifying amino silicone oil, which is marked as S-5.
Example 6
The diethyl maleate from example 5 was replaced by an equimolar portion of dioctyl maleate and the remaining steps were left unchanged to obtain a self-emulsifying amino silicone oil, noted S-6.
Example 7
Adding the self-emulsifying amino silicone oil S-1 obtained in the example 1 and methyl glycidyl ether into a reaction vessel according to the mol ratio of 1 to 2, adding anhydrous ethanol which is 5 times the weight of the self-emulsifying amino silicone oil S-1 and the methyl glycidyl ether and tetramethyl ammonium hydroxide which is 0.1 percent of the weight of the self-emulsifying amino silicone oil S-1 and the methyl glycidyl ether, reacting for 2 hours at 20 ℃, continuously heating to 55 ℃ for reacting for 2 hours, adding butyl chloroacetate which is 2 times the mol number of the self-emulsifying amino silicone oil S-1, reacting for 30 hours at 65 ℃, removing ethanol, and obtaining the self-emulsifying amino silicone oil which is marked as S-7.
Example 8
Adding the self-emulsifying amino silicone oil S-2 obtained in the example 2 and methyl glycidyl ether into a reaction vessel according to the mol ratio of 1.8 to 1, adding anhydrous ethanol which is 5 times the weight of the self-emulsifying amino silicone oil S-2 and the methyl glycidyl ether and tetramethyl ammonium hydroxide which is 0.1 percent of the weight of the self-emulsifying amino silicone oil S-2 and the methyl glycidyl ether, reacting for 2 hours at 20 ℃, continuously heating to 55 ℃ for reacting for 2 hours, adding chlorooctadecane which is 1.5 times the mol number of the self-emulsifying amino silicone oil S-2, reacting for 36 hours at 65 ℃, removing ethanol, and obtaining the self-emulsifying amino silicone oil which is marked as S-8.
Example 9
Self-emulsifying amino Silicone oil S-6 obtained in example 6 with epoxy polyether CH 3 O(CH 2 CH 2 O) 20.4 CH 2 (CHCH 2 O) is added into a reaction vessel according to the molar ratio of 1The base silicone oil S-6 and the epoxy polyether are reacted for 2 hours at the temperature of 20 ℃, the weight of the absolute ethyl alcohol which is 5.5 times of that of the epoxy polyether and the self-emulsifying amino silicone oil S-6 and the epoxy polyether are reacted for 3 hours at the temperature of 55 ℃, and the self-emulsifying amino silicone oil which is marked as S-9 is obtained.
Example 10
In example 9, after further heating to 55 ℃ and reacting for 3 hours, chlorooctadecane of 1 time of the mole number of the self-emulsifying amino silicone oil S-6 was added and reacted for 40 hours at 65 ℃, ethanol was removed, and the self-emulsifying amino silicone oil, which is recorded as S-10, was obtained.
Comparative example 1
Epoxy terminated polyether polysiloxane block copolymer R 5 SiCH 3 CH 3 O(SiOCH 3 CH 3 ) 67.4 SiCH 3 CH 3 R 5 (wherein R is 5 Is (OCH) 2 CH)O(CH 2 CH 2 O) 15.4 CH 2 CH 2 CH 2 -) and cyclohexylamine are mixed according to the mol ratio of 1 to 2, a double-end epoxy group polyether polysiloxane block copolymer and butyl acetate with the weight 5 times that of the cyclohexylamine are added, the mixture reacts for 2 hours at the temperature of 10 ℃, then the temperature is raised to 35 ℃ and the reaction is carried out for 2 hours, the butyl acetate is removed, and the self-emulsifying amino silicone oil is obtained and is marked as S-11.
Comparative example 2
In comparative example 1, after heating to 35 ℃ for reaction for 2 hours, cooling to 20 ℃, adding the epoxy polyether of example 9 having 1 time of the mole number of the epoxy-terminated polyether polysiloxane block copolymer, and tetramethylammonium hydroxide accounting for 0.1% of the weight of the epoxy polyether, continuing to react for 2 hours, heating to 55 ℃ for reaction for 3 hours, removing butyl acetate, and obtaining self-emulsifying amino silicone oil, which is marked as S-12.
Comparative example 3
In comparative example 2, after the temperature is raised to 55 ℃ and the reaction is carried out for 3 hours, chlorooctadecane with the mol number being 1 time of that of the double-end epoxy group polyether polysiloxane block copolymer is added, the reaction is carried out for 40 hours at 65 ℃, butyl acetate is removed, and the self-emulsifying amino silicone oil is obtained and is marked as S-13.
The preparation method of the amino silicone oil emulsion comprises the following steps: adding 65 parts of deionized water into 35 parts of self-emulsifying amino silicone oil under high-speed stirring of 900rpm, adjusting the pH value of the emulsion to 5.5-6 after stirring and dispersing, and obtaining the translucent blue-emitting to slightly opaque blue-emitting yellow microemulsion.
Fabric treatment: and preparing the amino silicone oil emulsion into a finishing agent of 30g/L to finish the pure cotton bleached cloth, adopting a double-dipping and double-rolling process, drying for 5min at the temperature of 100 ℃, and shaping for 30s at the temperature of 180 ℃.
Hydrophilicity test: after the fabric was spread horizontally, 1 drop of water was dropped from the fabric at a height of 2cm from the fabric using a standard dropper (25 drops/ml), and the time taken for the fabric to absorb 1 drop was observed. The shorter the water absorption time, the better the hydrophilicity.
Yellowing test: the whiteness value of the finished fabric was tested using a ColorQuest colorimeter and compared to the whiteness value of the unfinished fabric, the whiteness ratio = whiteness value of finished fabric/whiteness value of fabric before finish x 100%.
Irradiation yellowing series: according to the method of GB/T30669-2014, a ColorQuest colorimetric instrument is adopted to test the wavelength of 340nm and the irradiance of 0.8W/(m) 2 Nm) ultraviolet irradiation for 60h, testing the whiteness value after irradiation, and testing the yellowing series by adopting a color chart.
Yellowing grade: 5 minutes, no yellowing at all; 4 min, slight yellowing (no obvious yellowing); slight yellowing (slightly obvious yellowing) for 3 minutes; 2 min, slightly severe yellowing (obvious yellowing); yellowing was very severe (very marked yellowing) for 1 point. Each test to be tested was tested on 10 pieces, and 1 evaluation score was taken from each of the 10 trained volunteers and retained one bit after the decimal point. The 10 fractions are averaged and retained one bit after the decimal point.
The results are shown in Table 1.
TABLE 1
From the results of table 1, it can be seen that the amino silicone oil emulsion obtained from the self-emulsifying amino silicone oil of the present application for the after-treatment of fabric can significantly improve the hydrophilicity of fabric, and the hydrophilicity is improved with the increase of hydrophilic groups.
In addition, compared with secondary amination of cyclohexylamine in comparative examples 1-3, secondary amination of primary amino groups by using dialkyl maleate in the application has lower activity of secondary amino groups, and the finished fabric has less yellowing and is more resistant to yellowing after irradiation.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The preparation method of the self-emulsifying amino silicone oil is characterized in that the self-emulsifying amino silicone oil is obtained by reacting double-amino-terminated polyether-polysiloxane-polyether block copolymer with dialkyl maleate;
the dialkyl maleate has a structure shown in a formula (1),
(1)
wherein R is 1 Selected from C1-C18 alkyl.
2. The method for preparing self-emulsifying amino-silicone oil according to claim 1, wherein the amino-terminated double-terminal polyether-polysiloxane-polyether block copolymer is obtained by reacting an amino-terminated polyether with an epoxy-terminated polysiloxane, or by reacting an amino-terminated polyether with an anhydride-terminated polysiloxane.
3. The method of claim 1, wherein the molar ratio of the amino-terminated double-terminal polyether-polysiloxane-polyether block copolymer to the dialkyl maleate is 1.
4. The self-emulsifying aminosilicone of claim 1A process for the preparation of an oil, characterized in that R is 1 Selected from C4-C12 alkyl.
5. The method for preparing self-emulsifying amino silicone oil according to claim 1, wherein the reaction of the amino-terminated polyether-polysiloxane-polyether block copolymer with dialkyl maleate further comprises the following steps: carrying out quaternization reaction.
6. The method for preparing self-emulsifying amino-silicone oil according to claim 5, wherein the quaternization reaction is performed by adding epichlorohydrin.
7. The method for preparing self-emulsifying amino-silicone oil according to claim 5, wherein the quaternization is carried out by adding an epoxy group-containing compound to carry out a ring-opening reaction and then adding a halogenating agent to carry out a reaction.
8. The method of claim 7, wherein the epoxy group-containing compound is selected from the group consisting of C1-C14 alkyl glycidyl ethers and compounds of the formula R 2 O(CH 2 CH 2 O) a (CH 2 CHCH 3 O) b CH 2 (CHCH 2 O) one or more of epoxy polyether, wherein R 2 Selected from H, C1-C20 alkyl or C1-C20 substituted alkyl, a =1-100, b =0-100.
9. The method for preparing self-emulsifying amino silicone oil according to claim 7, wherein the halogenating agent is one or more selected from the group consisting of chlorinated organic compounds, brominated organic compounds and iodinated organic compounds.
10. An amino silicone oil emulsion obtained from the self-emulsifying amino silicone oil prepared by the preparation method according to any one of claims 1 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310044130.4A CN115975205B (en) | 2023-01-29 | 2023-01-29 | Preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310044130.4A CN115975205B (en) | 2023-01-29 | 2023-01-29 | Preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115975205A true CN115975205A (en) | 2023-04-18 |
CN115975205B CN115975205B (en) | 2023-11-17 |
Family
ID=85972268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310044130.4A Active CN115975205B (en) | 2023-01-29 | 2023-01-29 | Preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115975205B (en) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001005870A1 (en) * | 1999-07-19 | 2001-01-25 | Bayer Aktiengesellschaft | Polycarbonates containing aspartic acid ester-functional silicones |
CN1299840A (en) * | 1999-12-13 | 2001-06-20 | 拜尔公司 | Water-proof-performance gifting using carboxy-contained polyorganosiloxane |
CN102942697A (en) * | 2012-10-22 | 2013-02-27 | 浙江安诺其助剂有限公司 | Preparation method of main chain hydrophilic modified amino silicone oil |
US20130267654A1 (en) * | 2010-12-21 | 2013-10-10 | Wacker Chemie Ag | Silicone aspartate copolymers |
CN103483593A (en) * | 2013-09-23 | 2014-01-01 | 上海硅普化学品有限公司 | Polyether polyamine, preparation method of polyether polyamine, polyether polyamine block silicone oil and preparation method of polyether polyamine block silicone oil |
CN106146856A (en) * | 2016-08-03 | 2016-11-23 | 清远市宏图助剂有限公司 | A kind of terpolymer block hydrophilic amino silicone oil and its preparation method and application |
CN106381715A (en) * | 2016-08-30 | 2017-02-08 | 浙江科峰有机硅有限公司 | Quaternary ammonium modified block polyether/amino silicone oil and preparation method thereof |
CN108219147A (en) * | 2018-01-04 | 2018-06-29 | 佛山市三水古闰纺织印染研究院有限公司 | A kind of preparation method of hydrophilic silicone oil |
CN108774322A (en) * | 2018-06-26 | 2018-11-09 | 湖北新海鸿化工有限公司 | A kind of preparation method of fabric softener |
CN108951170A (en) * | 2018-07-28 | 2018-12-07 | 黄勇 | A kind of preparation method of color inhibition hydrophilic smoothing agent for fabric |
US20210363307A1 (en) * | 2018-10-19 | 2021-11-25 | Momentive Performance Materials Gmbh | Aspartic acid ester-functional polysiloxanes, their preparation and use thereof |
-
2023
- 2023-01-29 CN CN202310044130.4A patent/CN115975205B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001005870A1 (en) * | 1999-07-19 | 2001-01-25 | Bayer Aktiengesellschaft | Polycarbonates containing aspartic acid ester-functional silicones |
CN1299840A (en) * | 1999-12-13 | 2001-06-20 | 拜尔公司 | Water-proof-performance gifting using carboxy-contained polyorganosiloxane |
US20130267654A1 (en) * | 2010-12-21 | 2013-10-10 | Wacker Chemie Ag | Silicone aspartate copolymers |
CN102942697A (en) * | 2012-10-22 | 2013-02-27 | 浙江安诺其助剂有限公司 | Preparation method of main chain hydrophilic modified amino silicone oil |
CN103483593A (en) * | 2013-09-23 | 2014-01-01 | 上海硅普化学品有限公司 | Polyether polyamine, preparation method of polyether polyamine, polyether polyamine block silicone oil and preparation method of polyether polyamine block silicone oil |
CN106146856A (en) * | 2016-08-03 | 2016-11-23 | 清远市宏图助剂有限公司 | A kind of terpolymer block hydrophilic amino silicone oil and its preparation method and application |
CN106381715A (en) * | 2016-08-30 | 2017-02-08 | 浙江科峰有机硅有限公司 | Quaternary ammonium modified block polyether/amino silicone oil and preparation method thereof |
CN108219147A (en) * | 2018-01-04 | 2018-06-29 | 佛山市三水古闰纺织印染研究院有限公司 | A kind of preparation method of hydrophilic silicone oil |
CN108774322A (en) * | 2018-06-26 | 2018-11-09 | 湖北新海鸿化工有限公司 | A kind of preparation method of fabric softener |
CN108951170A (en) * | 2018-07-28 | 2018-12-07 | 黄勇 | A kind of preparation method of color inhibition hydrophilic smoothing agent for fabric |
US20210363307A1 (en) * | 2018-10-19 | 2021-11-25 | Momentive Performance Materials Gmbh | Aspartic acid ester-functional polysiloxanes, their preparation and use thereof |
Non-Patent Citations (2)
Title |
---|
汤金伟;刘锦凡;方伟洪;程文静;郑成;: "亲水嵌段硅油整理剂的合成研究", 有机硅材料, vol. 32, no. 04, pages 274 - 278 * |
袁洁 等: "亲水改性三元嵌段共聚有机硅柔软剂的合成", 印染, vol. 42, no. 15, pages 10 - 15 * |
Also Published As
Publication number | Publication date |
---|---|
CN115975205B (en) | 2023-11-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2717942B2 (en) | Non-yellowing fabric soft finish using a composition comprising a polyorganosiloxane | |
KR100517103B1 (en) | Nitrogen Atom-Containing Polysiloxanes, Their Preparation, and Fiber and Fabric Finishing Agent Compositions | |
US8916511B2 (en) | Polysiloxanes having quaternary ammonium groups and use thereof | |
US5025076A (en) | Silicone-based fabric finishing agent | |
US4757121A (en) | Silicone-based softening agent for synthetic fibers | |
CN101565896B (en) | Quaternary amino cation modified polysiloxane softening agent and preparation method thereof | |
KR101423649B1 (en) | Textile softener base on self-emulsified type silicone oil | |
US20080221276A1 (en) | Silicone-containing graft copolymers of blockwise structure | |
CN107129578B (en) | Preparation method of amino modified silicone oil finishing agent with net structure | |
EP0441530B1 (en) | Method of treating fibrous materials | |
US6255429B1 (en) | Amine-, polyol-, amide-functional siloxane copolymers and methods for their preparation | |
CN105949468B (en) | A kind of anionic is linearly copolymerized the preparation method of organosilicon flexible finishing agent | |
EP0399706B1 (en) | Method of treating fibrous materials | |
CN102021838B (en) | Low-yellowing organic silicon softener, preparation method and application thereof | |
CN109810253A (en) | A kind of both-end epoxy group Siloxane-Oxyalkylene Copolymers and the preparation method and application thereof | |
CN109880107A (en) | The polysiloxane compound and its preparation and application that polyethers and quaternary ammonium cation are modified | |
EP3751048A1 (en) | Fiber-treating agent | |
CN115975205A (en) | Preparation method of self-emulsifying amino silicone oil and amino silicone oil emulsion | |
US20090068911A1 (en) | Amino-Mercapto Functional Organopolysiloxanes | |
KR101003798B1 (en) | Hydrophilic amino modified polysiloxane and method for preparing thereof | |
JPH0912723A (en) | Polyether-modified polyorganosiloxane | |
CA2449955A1 (en) | Polysiloxane and textile adjunct comprising a polysiloxane | |
CN113248713B (en) | Low-yellowing amino silicone oil and preparation method and application thereof | |
CN113549220A (en) | Modified hydrogen-containing silicone oil and preparation method and application thereof | |
KR101284152B1 (en) | Silicon copolymer, its manufacturing method and fabric softner using the same |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |