CN115975205B - 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
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- 229920013822 aminosilicone Polymers 0.000 title claims abstract description 80
- 239000000839 emulsion Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 65
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 62
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 43
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims description 54
- -1 polysiloxane Polymers 0.000 claims description 41
- 239000004593 Epoxy Substances 0.000 claims description 35
- 229920001296 polysiloxane Polymers 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229920001400 block copolymer Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000007142 ring opening reaction 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
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004383 yellowing Methods 0.000 abstract description 26
- 239000004744 fabric Substances 0.000 abstract description 21
- 239000000675 fabric finishing Substances 0.000 abstract description 2
- 238000009962 finishing (textile) Methods 0.000 abstract description 2
- 238000009988 textile finishing Methods 0.000 abstract description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 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
- 125000003277 amino group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 125000001302 tertiary amino group Chemical group 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-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
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 3
- 230000002140 halogenating effect Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 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
- 239000000203 mixture Substances 0.000 description 2
- 230000009257 reactivity 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940009098 aspartate Drugs 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-L aspartate group Chemical group N[C@@H](CC(=O)[O-])C(=O)[O-] CKLJMWTZIZZHCS-REOHCLBHSA-L 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
- 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
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002118 epoxides Chemical group 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
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007493 shaping process 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
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Abstract
The application relates to the technical field of textile 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 a double-end amino end capped polyether-polysiloxane-polyether segmented copolymer with dialkyl maleate. Preferably, quaternization may also be carried out. The amino silicone oil emulsion obtained by the self-emulsifying amino silicone oil can be used as a fabric finishing agent to endow fabrics with low yellowing, antistatic property, softness and other properties.
Description
Technical Field
The application relates to the technical field of textile 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 the fabric with smooth and fluffy hand feeling. Conventional aminosilicone emulsions are primary amino groups but tend to cause yellowing of the fabric. Changing the primary amino groups in the amino silicone oil emulsion to secondary amino groups can reduce the yellowing of the fabric.
Disclosure of Invention
The inventor considers that the prior secondary amino silicone oil emulsion can further reduce the yellowing of fabrics, and through a great deal of analysis, test and research, the inventor discovers an amino silicone oil emulsion finishing agent capable of obviously reducing the yellowing of the fabrics, and the application is provided.
The application adopts the following technical scheme:
a preparation method of self-emulsifying amino silicone oil is obtained by reacting a double-end amino end capped polyether-polysiloxane-polyether segmented copolymer with dialkyl maleate;
the dialkyl maleate has a structure as shown in formula (1),
wherein R is 1 Selected from C1-C18 alkyl.
Preferably, the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer is obtained by reacting double-end amino polyether with double-end epoxy polysiloxane or by reacting double-end amino polyether with double-end anhydride polysiloxane.
Preferably, the molar ratio of the double-end amino-terminated polyether-polysiloxane-polyether block copolymer to the dialkyl maleate is 1:2-10.
Preferably, said R 1 Selected from C4-C12 alkyl.
Preferably, after the reaction of the double-end amino-terminated polyether-polysiloxane-polyether block copolymer and the dialkyl maleate, the method further comprises the following steps: and (5) carrying out quaternization reaction.
More preferably, the quaternization reaction is performed by adding epichlorohydrin.
More preferably, the quaternization reaction is carried out by adding a compound containing epoxy groups for ring opening reaction and then adding a halogenated reagent for reaction.
Further preferred, 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 polyethers, wherein R 2 Selected from H, C-C20 alkyl or C1-C20 substituted alkyl, a=1-100, b=0-100.
Further preferably, the halogenated agent is selected from one or more of chlorinated organic compounds, brominated organic compounds and iodinated organic compounds.
An amino silicone oil emulsion obtained by self-emulsifying amino silicone oil obtained by the preparation method according to any one of the above embodiments.
In summary, the application has the following beneficial effects:
1. the self-emulsifying amino silicone oil provided by the application is linear amino silicone oil, has a good effect, forms a secondary amino group after the primary amino group of the end group reacts with dialkyl maleate, and has low activity due to the surrounding and steric hindrance effects of an aspartate structure and the electron-withdrawing effect of the aspartate, so that yellowing is not easy to occur.
2. It has further been found in the present application that the alkyl groups in the dialkyl maleates are C4-C12 alkyl groups and that the secondary amino groups in the self-emulsifying amino silicone oils of the present application are less reactive, possibly due to steric shielding as well as hydrophobic effects of the C4-C12 alkyl groups.
3. The self-emulsifying amino silicone oil can be further subjected to tertiary amination and/or quaternization, and the yellowing resistance of the amino silicone oil emulsion can be improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning 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 application belongs. In case of conflict, the present specification will control.
The application provides a preparation method of self-emulsifying amino silicone oil, which is obtained by reacting a double-end amino end capped polyether-polysiloxane-polyether segmented copolymer with dialkyl maleate;
the above dialkyl maleate has a structure as shown in formula (1),
wherein R is 1 Selected from C1-C18 alkyl.
In the application, the double-end amino group of the double-end amino group end capped polyether-polysiloxane-polyether segmented copolymer is a primary amino group, the double-end amino group end capped polyether-polysiloxane-polyether segmented copolymer reacts with dialkyl maleate to generate Michael addition reaction between amino group and carbon-carbon unsaturated double bond, the primary amino group is converted into a secondary amino group, and the structure formed by the reaction between the primary amino group and dialkyl maleate is shown as the following formula (2).
The effect is that the activity of the secondary amino group is low, and yellowing is not easy to occur.
In a preferred embodiment of the application, the double amino-terminated polyether-polysiloxane-polyether block copolymer is obtained by reacting a double amino polyether with a double epoxy polysiloxane or by reacting a double amino polyether with a double anhydride polysiloxane.
In the present application, the double-amino polyether is hydrophilic polyether, and one of the double-amino polyether has the chemical general 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, and m is larger than or equal to n. The chemical structural general formula of the double-end epoxy 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 Representative (OCH) 2 CH)OCH 2 CH 2 CH 2 -，R 4 Selected from methyl, phenyl, 3-trifluoropropyl, 3-chloropropyl, etc., x=10-200. The double-ended epoxy polysiloxanes of the present application can be obtained by hydrosilylation of the corresponding hydrogen-terminated polysiloxanes with allyl glycidyl ether, as is well known to those skilled in the art.
The reactivity of amino groups with epoxy groups is high. The application adopts hydrophilic double-end amino polyether and double-end epoxy polysiloxane to carry out ring opening reaction to obtain linear amino silicone oil. Specifically, the molar ratio of the double-ended aminopolyether to the double-ended epoxy polysiloxane may be 1.3-2.2:1, or, further, the molar ratio of the double-ended aminopolyether to the double-ended epoxy polysiloxane may be 1.8-2.1:1, for example, the molar ratio may be 1.8:1, 1.85:1, 1.9:1, 1.93:1, 1.95:1, 1.97:1, 2:1, 2.01:1, 2.02:1, 2.03:1, 2.04:1, 2.05:1, or the like.
In the application, the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer can also be obtained by reacting double-end amino polyether with double-end anhydride polysiloxane, wherein double-end anhydride polysiloxane refers to that double-end groups of polysiloxane are acid anhydride groups. The amino group can undergo a ring-opening reaction with the anhydride to form an amide and a carboxyl group. Specifically, the molar ratio of the double-end amino polyether to the double-end anhydride polysiloxane can be 1.8-2.2:1, and for example, the molar ratio can be 1.8:1, 1.85:1, 1.9:1, 1.93:1, 1.95:1, 1.97:1, 2:1, 2.01:1, 2.02:1, 2.03:1, 2.04:1, 2.05:1, and the like.
In a preferred embodiment of the application, the molar ratio of the double amino-terminated polyether-polysiloxane-polyether block copolymer to the dialkyl maleate is from 1:2 to 10. More preferably, the molar ratio of the double-ended polyether-polysiloxane-polyether block copolymer to the dialkyl maleate is from 1:2 to 3.5.
By the above embodiment, the double-ended amino groups are all 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 application, R 1 Selected from C4-C12 alkyl. R is R 1 When the amino is C4-C12 alkyl, the C4-C12 has a certain space shielding effect and a certain hydrophobic effect, and the yellowing resistance of the secondary amine group is further improved. But R is 1 The carbon chain of the amino silicone oil is not suitable to be too long, and the hydrophilicity of the amino silicone oil is reduced due to the strong hydrophobic effect, so that self-emulsification cannot be realized.
In a preferred embodiment of the present application, the reaction of the double amino-terminated polyether-polysiloxane-polyether block copolymer with the dialkyl maleate further comprises the steps of: and (5) carrying out quaternization reaction. When the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer is obtained by reacting double-end amino polyether with double-end epoxy polysiloxane, ring opening reaction is carried out on epoxy groups and amino groups to form a secondary amino structure (secondary amino 1), the reactivity of the secondary amino 1 is higher than that of a secondary amino group (secondary amino 2) obtained by primary amino and dialkyl maleate, quaternization reaction is easier to carry out, but because the secondary amino 1 is in the inside of a linear chain molecular structure, the anti-yellowing performance is better due to space shielding effect. The secondary amino 1 is quaternized, so that the hydrophilicity of amino silicone oil can be improved, self-emulsification can be better realized, and the antibacterial and antibacterial effects and better softness and antistatic properties can be provided for fabrics and the like.
In a more preferred embodiment of the present application, the quaternization is by adding epichlorohydrin. The secondary amino 1 can directly react with epoxy chloropropane to obtain a quaternary ammonium salt structure, and the specific molar ratio of the self-emulsifying amino silicone oil to the epoxy chloropropane is 1:1.5-5. Further, the reaction condition can be an absolute ethanol 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 be added as an accelerator.
In a more preferred embodiment of the present application, the quaternization is carried out by adding a compound containing an epoxy group for ring opening and then adding a halogenating agent for reaction. The secondary amino 1 can be subjected to ring opening reaction with the compound containing the epoxy group to form a tertiary amine group, and the tertiary amine group is subjected to quaternization reaction. Specifically, when the self-emulsifying amino silicone oil and the epoxy group compound are subjected to ring opening reaction, the molar ratio of the self-emulsifying amino silicone oil to the epoxy group compound is 1:0.3-5, the reaction temperature can be 15-60 ℃, and the reaction time can be 1-5 hours. When the self-emulsifying amino silicone oil and the halogenated reagent are subjected to quaternization reaction, the molar ratio of the self-emulsifying amino silicone oil to the halogenated reagent can be 1:0.3-4, the reaction temperature can be 50-80 ℃, and the reaction time can be 10-40 hours.
The secondary amino 1 is subjected to ring opening reaction with the compound containing the epoxy group, so that the secondary amino 1 is partially or completely converted into tertiary amino groups, and the yellowing resistance of the tertiary amino groups is better than that of the secondary amino 1. And then a part or all of tertiary amine groups are converted into quaternary ammonium salts by a halogenating reagent.
In a further preferred embodiment of the application, the epoxide group-containing compound is selected from C1-C14-alkyl glycidyl ethers and has 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 polyethers, wherein R 2 Selected from H, C-C20 alkyl or C1-C20 substituted alkyl, a=1-100, b=0-100. C1-C14 alkyl glycidyl ethersCan be subjected to ring-opening reaction with secondary amino 1 to form tertiary amino group, and even more 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 react with secondary amino 1 to form tertiary amino group, and even more preferably, the epoxy polyether is hydrophilic epoxy polyether, so that the hydrophilicity of self-emulsifying amino silicone oil can be improved, and the self-emulsifying performance can be improved.
In a further preferred embodiment of the present application, the halogenated 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, etc.
In another aspect, the application provides an amino silicone oil emulsion obtained by self-emulsifying amino silicone oil prepared by the preparation method of any one of the embodiments.
The amino silicone oil emulsion of the application can be prepared as follows: under the intense stirring, adding a certain amount of water into the self-emulsifying amino silicone oil, stirring and dispersing, and regulating the pH value of the system to 5.5-6. The amino silicone oil emulsion of the present application is a transparent to translucent blue-emitting microemulsion or a slightly opaque blue-emitting microemulsion, and the solid content may be 5 to 50wt%, or further, the solid content of the amino silicone oil emulsion may be 10 to 40wt%.
The technical scheme of the present application will be described in detail with reference to examples, comparative examples and experimental data.
Unless otherwise indicated, the parts in the examples and comparative examples below are parts by weight.
Description of raw materials
Double-ended amino polyether 1: NH (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 represents CH 2 CHCH 3 O；
Double-ended amino polyether 2: NH (NH) 2 CH 2 CH 2 O(EO) 15.7 CH 2 CH 2 NH 2 ；
Double-ended epoxy polysiloxane 1: r is R 3 Si(CH 3 ) 2 O(SiCH 3 CH 3 O) 45.9 Si(CH 3 ) 2 R 3 ，R 3 Representative (OCH) 2 CH)OCH 2 CH 2 CH 2 -；
Double-ended epoxy polysiloxane 2: r is R 3 Si(CH 3 ) 2 O(SiCH 3 CH 3 O) 70.4 Si(CH 3 ) 2 R 3 ，R 3 Representative (OCH) 2 CH)OCH 2 CH 2 CH 2 -；
Preparation example 1
Adding the double-end amino polyether 1 and the double-end epoxy polysiloxane 1 into a reaction vessel according to a molar ratio of 1.9:1, adding butyl acetate which is 4 times by weight of the double-end amino polyether 1 and the double-end epoxy polysiloxane 1, stirring and reacting for 2 hours at 15 ℃, heating to 50 ℃ and continuously reacting for 2 hours, and removing the butyl acetate to obtain the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer which is marked as P-1.
Preparation example 2
Adding the double-end amino polyether 1 and the double-end epoxy polysiloxane 2 into a reaction vessel according to a molar ratio of 2:1, adding butyl acetate which is 5 times by weight of the double-end amino polyether 1 and the double-end epoxy polysiloxane 2, stirring and reacting for 2 hours at 15 ℃, heating to 50 ℃ and continuously reacting for 2.5 hours, and removing the butyl acetate to obtain the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer which is marked as P-2.
Preparation example 3
Adding the double-end amino polyether 2 and the double-end epoxy polysiloxane 1 into a reaction vessel according to a molar ratio of 1.95:1, adding tetrahydrofuran which is 4 times by weight of the double-end amino polyether 2 and the double-end epoxy polysiloxane 1, stirring and reacting for 2 hours at 15 ℃, heating to 50 ℃ and continuing to react for 2 hours, and removing the tetrahydrofuran to obtain the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer which is marked as P-3.
Preparation example 4
Adding the double-end amino polyether 2 and the double-end epoxy polysiloxane 2 into a reaction vessel according to a molar ratio of 2:1, adding tetrahydrofuran which is 4 times the weight of the double-end amino polyether 2 and the double-end epoxy polysiloxane 2, stirring and reacting for 2 hours at 15 ℃, heating to 50 ℃ and continuing to react for 2.5 hours, and removing the tetrahydrofuran to obtain the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer which is marked as P-4.
Example 1
The double-end amino-terminated polyether-polysiloxane-polyether segmented copolymer P-1 and dimethyl maleate of the preparation example 1 are mixed according to the mol ratio of 1:2.02, sodium methoxide with the weight sum of P-1 and dimethyl maleate of 0.03 percent is added, the temperature is raised to 90 ℃ under the protection of nitrogen for reaction for 36 hours, unreacted dimethyl maleate is removed under reduced pressure, and the self-emulsifying amino silicone oil which is marked as S-1 is obtained.
Example 2
The dimethyl maleate in example 1 was replaced with an equimolar portion of dihexyl maleate, the rest of the procedure remaining unchanged, obtaining a self-emulsifying aminosilicone, designated S-2.
Example 3
The double-end amino end capped polyether-polysiloxane-polyether segmented copolymer P-2 and dioctyl maleate of the preparation example 2 are mixed according to the mol ratio of 1:2, sodium methoxide with the total weight of P-2 and dioctyl maleate accounting for 0.03 percent is added, the temperature is raised to 90 ℃ for reaction for 30 hours under the protection of nitrogen, unreacted dioctyl maleate is removed under reduced pressure, and the self-emulsifying amino silicone oil is obtained and is marked as S-3.
Example 4
The double-end amino end capped polyether-polysiloxane-polyether segmented copolymer P-3 and dibutyl maleate of the preparation example 3 are mixed according to the mol ratio of 1:2.05, sodium methoxide with the total weight of P-3 and dibutyl maleate accounting for 0.03 percent is added, the temperature is raised to 90 ℃ to react for 40 hours under the protection of nitrogen, unreacted dibutyl maleate is removed under reduced pressure, and the self-emulsifying amino silicone oil which is marked as S-4 is obtained.
Example 5
The double-end amino end capped polyether-polysiloxane-polyether segmented copolymer P-4 and diethyl maleate of the preparation example 4 are mixed according to the mol ratio of 1:2.05, sodium methoxide with the total weight of P-4 and diethyl maleate accounting for 0.03 percent is added, the temperature is raised to 90 ℃ for reaction for 40 hours under the protection of nitrogen, unreacted diethyl maleate is removed under reduced pressure, and the self-emulsifying amino silicone oil is obtained and is marked as S-5.
Example 6
The diethyl maleate of example 5 was replaced with an equimolar fraction of dioctyl maleate, the rest of the procedure remaining unchanged, obtaining a self emulsifying aminosilicone, designated S-6.
Example 7
The self-emulsifying aminosilicone S-1 obtained in example 1 and methyl glycidyl ether were added in a molar ratio of 1:2 to a reaction vessel, anhydrous ethanol and 5 times the weight of the self-emulsifying aminosilicone S-1 and methyl glycidyl ether and tetramethyl ammonium hydroxide 0.1% were added, the reaction was continued at 20℃for 2 hours, the temperature was raised to 55℃for 2 hours, butyl chloroacetate 2 times the number of moles of the self-emulsifying aminosilicone S-1 was added, the reaction was carried out at 65℃for 30 hours, and ethanol was removed to obtain the self-emulsifying aminosilicone, designated as S-7.
Example 8
The self-emulsifying aminosilicone S-2 obtained in example 2 and methyl glycidyl ether were added in a molar ratio of 1:1.8 to a reaction vessel, anhydrous ethanol in an amount of 5 times the weight of the self-emulsifying aminosilicone S-2 and methyl glycidyl ether and tetramethyl ammonium hydroxide in an amount of 0.1% by weight of the self-emulsifying aminosilicone S-2 and methyl glycidyl ether were added, the reaction was continued at 20℃for 2 hours, the temperature was raised to 55℃for 2 hours, chlorooctadecane in an amount of 1.5 times the molar ratio of the self-emulsifying aminosilicone S-2 was added, the ethanol was removed, and the self-emulsifying aminosilicone was obtained, designated as S-8, by reacting at 65℃for 36 hours.
Example 9
The self-emulsifying aminosilicone S-6 obtained in example 6 was reacted with an epoxy polyether CH 3 O(CH 2 CH 2 O) 20.4 CH 2 (CHCH 2 O) adding the mixture into a reaction vessel according to the mol ratio of 1:1, adding anhydrous ethanol which is 5.5 times the weight of the self-emulsifying amino silicone oil S-6 and the epoxy polyether and tetramethyl ammonium hydroxide which is 0.1% of the weight of the self-emulsifying amino silicone oil S-6 and the epoxy polyether, and heating the mixture at 20 DEG CThe reaction was continued for 2 hours and the temperature was raised to 55℃for 3 hours to obtain self-emulsifying aminosilicone, designated S-9.
Example 10
In example 9, after the reaction was continued at 55℃for 3 hours, 1-fold mol of chlorooctadecane was added to self-emulsifying aminosilicone S-6, and the reaction was carried out at 65℃for 40 hours to remove ethanol, thereby obtaining self-emulsifying aminosilicone designated S-10.
Comparative example 1
Double-end epoxy 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 Mixing (-) and cyclohexylamine according to a molar ratio of 1:2, adding the double-end epoxy polyether polysiloxane block copolymer and 5 times of the weight of the cyclohexylamine and butyl acetate, reacting for 2 hours at 10 ℃, heating to 35 ℃ and reacting for 2 hours, removing the butyl acetate, and obtaining self-emulsifying amino silicone oil which is marked as S-11.
Comparative example 2
In comparative example 1, after the reaction time was 2 hours at 35 ℃, the temperature was lowered to 20 ℃, the epoxy polyether in example 9, which was 1 time the mole number of the double-ended epoxy polyether polysiloxane block copolymer, and tetramethyl ammonium hydroxide, which was 0.1% by weight of the double-ended epoxy polyether polysiloxane block copolymer and the epoxy polyether, were added, the reaction was continued for 2 hours, the reaction time was further raised to 55 ℃ for 3 hours, butyl acetate was removed, and self-emulsifying amino silicone oil was obtained, which was designated as S-12.
Comparative example 3
In comparative example 2, after the reaction was continued for 3 hours at 55℃the double-ended epoxy polyether polysiloxane block copolymer was added with 1-fold mol of chlorooctadecane and reacted at 65℃for 40 hours to remove butyl acetate to give a self-emulsifying aminosilicone, designated S-13.
The preparation method of the amino silicone oil emulsion comprises the following steps: under high-speed stirring at 900rpm, 65 parts of deionized water is added into 35 parts of self-emulsifying amino silicone oil, and after stirring and dispersing, the pH value of the emulsion is adjusted to 5.5-6, so that the semi-transparent blue-light-emitting to slightly opaque blue-yellow-light-emitting microemulsion is obtained.
And (3) fabric treatment: preparing the amino silicone oil emulsion into a finishing agent of 30g/L, finishing the pure cotton bleached cloth, adopting a two-dipping and two-bundling process, drying for 5min at 100 ℃, and shaping for 30s at 180 ℃.
Hydrophilicity test: after the fabric was spread horizontally, 1 drop of water was dropped from the high-phase fabric 2cm from the fabric using a standard dropper (25 drops/ml), and the time taken for the fabric to absorb 1 drop of water 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 colorimetric instrument and compared with the whiteness value of the fabric before finishing, the whiteness ratio = the whiteness value of the finished fabric/the whiteness value of the fabric before finishing x 100%.
Irradiation yellowing progression: according to the method of GB/T30689-2014, a ColorQuest colorimeter is adopted to test the irradiance of 0.8W/(m) with the wavelength of 340nm 2 Nm) ultraviolet light is irradiated for 60 hours, the whiteness value after irradiation is tested, and the yellowing grade number is tested by using a color chart.
Yellowing grade: 5 minutes, no yellowing at all; 4 minutes, slight yellowing (no obvious yellowing); 3 minutes, slight yellowing (slightly obvious yellowing); 2 minutes, the yellowing is slightly serious (obvious yellowing); 1 minute, the yellowing was severe (the yellowing was very pronounced). Each test to be tested was 10 pieces and 1 piece of evaluation score was taken by each of the 10 trained volunteers and kept to the decimal place later. The 10 scores are averaged and retained one after the decimal point.
The results are shown in Table 1.
TABLE 1
From the results in table 1, it is clear that the self-emulsifying amino silicone oil of the present application can significantly improve the hydrophilicity of the fabric when used for the after-finishing of the fabric, and the hydrophilicity is improved with the increase of hydrophilic groups.
In addition, compared with comparative examples 1-3, the secondary amination of the primary amino group is carried out by adopting the dialkyl maleate, the activity of the secondary amino group is lower, the yellowing of the finished fabric is less, and the fabric is more resistant to the yellowing after irradiation.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. A preparation method of self-emulsifying amino silicone oil is characterized in that the self-emulsifying amino silicone oil is obtained by reacting a double-end amino end capped polyether-polysiloxane-polyether segmented copolymer with dialkyl maleate;
the dialkyl maleate has a structure as shown in formula (1),
（1）
wherein R is 1 Selected from C4-C12 alkyl;
the molar ratio of the double-end amino end capped polyether-polysiloxane-polyether segmented copolymer to the dialkyl maleate is 1:2-10.
2. The method for preparing self-emulsifying amino silicone oil according to claim 1, wherein the double-amino-terminated polyether-polysiloxane-polyether block copolymer is obtained by reacting double-amino polyether with double-epoxy polysiloxane or by reacting double-amino polyether with double-anhydride polysiloxane.
3. The method for preparing self-emulsifying aminosilicone as defined in claim 1, wherein after reacting the double amino terminated polyether-polysiloxane-polyether block copolymer with a dialkyl maleate, further comprising the steps of: and (5) carrying out quaternization reaction.
4. A method for preparing a self-emulsifying aminosilicone as defined in claim 3 wherein the quaternization is by adding epichlorohydrin.
5. The method for preparing self-emulsifying amino silicone oil according to claim 3, wherein the quaternization reaction is carried out by adding a compound containing an epoxy group for ring-opening reaction and then adding a halogenated reagent for reaction.
6. The method for preparing self-emulsifying amino silicone oil according to claim 5, wherein the epoxy group-containing compound is selected from C1-C14 alkyl glycidyl ethers and compounds of 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 polyethers, wherein R 2 Selected from H, C-C20 alkyl or C1-C20 substituted alkyl, a=1-100, b=0-100.
7. The method for preparing self-emulsifying amino silicone oil according to claim 5, wherein the halogenated agent is one or more selected from the group consisting of chlorinated organic compounds, brominated organic compounds and iodinated organic compounds.
8. Amino silicone oil emulsion, characterized in that it is obtained from self-emulsifying amino silicone oils obtained by the preparation process according to any one of claims 1 to 7.
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