CN106700083B - A kind of polyquaternary amine base glucose polydimethylsiloxane polyether and preparation method thereof and hand feel finishing agent - Google Patents
A kind of polyquaternary amine base glucose polydimethylsiloxane polyether and preparation method thereof and hand feel finishing agent Download PDFInfo
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- -1 polydimethylsiloxane Polymers 0.000 title claims abstract description 134
- 229920000570 polyether Polymers 0.000 title claims abstract description 95
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 94
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 83
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 80
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 56
- 239000008103 glucose Substances 0.000 title claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000003277 amino group Chemical group 0.000 title abstract description 5
- 239000007858 starting material Substances 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 103
- 238000006243 chemical reaction Methods 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- QEQBINKVWYLHGD-BTVCFUMJSA-N methanamine;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound NC.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O QEQBINKVWYLHGD-BTVCFUMJSA-N 0.000 claims description 32
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 30
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 27
- 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 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 22
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 16
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 239000012875 nonionic emulsifier Substances 0.000 claims description 13
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000005639 Lauric acid Substances 0.000 claims description 7
- 229940070765 laurate Drugs 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims 3
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 35
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000839 emulsion Substances 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 12
- 229920005573 silicon-containing polymer Polymers 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229920000742 Cotton Polymers 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 39
- 229920002545 silicone oil Polymers 0.000 description 27
- 238000004383 yellowing Methods 0.000 description 26
- 239000007787 solid Substances 0.000 description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 229920013822 aminosilicone Polymers 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000009960 carding Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000004759 spandex Substances 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether 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
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
Invention provides a kind of hand feel finishing agent of polyquaternary amine base glucose polydimethylsiloxane polyether and its preparation method and application the polyquaternary amine base polyethers dimethyl silicone polymer.The polyquaternary amine base glucose polydimethylsiloxane polyether is indicated with general formula I.It is selected by synthesis technology route and starting material, so that the apparent state of film forming of hand feel finishing agent of the present invention from currently available technology liquid or hemicolloid state be transformed into solid-state or elastomer solid-state, after revolutionizing previous organic silicon emulsion arrangement, fabric sense of touch " oiliness " is overweight, so that unnatural, the uncomfortable technical problem of " viscous hand " personal clothing.Therefore, hand feel finishing agent of the present invention imparts the new sense of touch of fabric again: dry and comfortable tack-free, dry and comfortable, natural fine and smooth pro-skin, silk quality are soft and smooth, at the same assign cotton fiber fabric moment it is hydrophilic, without hot xanthochromia, the beneficial function such as no phenol xanthochromia.
Description
Technical Field
The invention relates to the field of functional finishing agents for textiles, in particular to polyquaternary ammonium group glucose polydimethylsiloxane polyether, a preparation method thereof and a hand feeling finishing agent.
Background
Currently, the development of global textile silicone materials has undergone four stages of development:
the first stage is a hydroxyl silicone oil emulsion and a methyl silicone oil emulsion, and the structural characteristics are as follows:
hydroxyl silicone oil:wherein n is 1-100000;
methyl silicone oil:wherein m is 1 to 100000.
The second stage is amino silicone oil emulsion, and the structural characteristics are as follows:
wherein: m is 1-10000; n is 1-50; r1 ═ C3H6NH2，-C3H6NHC2H4NH2。
The third stage is polyether silicone oil and polyether modified amino silicone oil, and the structural characteristics are as follows:
polyether silicone oil:
wherein m is 1-100000, and n is 1-50; r2 ═ C3H6O-(C3H6O)a-(C2H4O)b-H a＝2～10；b＝5～50；
Polyether modified amino silicone oil: MM capping
Wherein m is 5-500; n is 1-50; r3 ═ C3H6NH(C3H6O)a-(C2H4O)b-H a＝2～10；b＝5～50。
The fourth stage is amino polyether block silicone oil, and the structural characteristics are as follows:
amino polyether block silicone oil:
wherein a is 1-20, b is 1-60, m is 1-250, and p is 1-100; r1＝-CH3，-C2H5，C4H9，-H。
The applicant has conducted a great deal of research on the above-mentioned four-stage silicone materials and obtained the contribution ratios of the main constituent materials listed in table 1 to the respective properties, and the main property comparisons of the generations of silicone materials listed in table 2.
TABLE 1 proportion of contribution of main component materials of organosilicon materials to each property at each stage
TABLE 2 comparison of the main Properties of the organosilicon materials at the stages
And (4) conclusion: can be extracted according to the table I and the table II:
① Silicone oil materials from the first to fourth generations impart a tactile function to the fabric, primarily the chain links of polydimethylsiloxane polymersBy controlling polydimethyl siliconThe molecular weight of the siloxane chain link realizes the touch functions of fluffiness, softness, smoothness and the like, however, the chain link polymer has no ion, the adsorption quantity of the polymer is improved by introducing amino cationic groups, the directional adsorption behavior of the polymer is changed, the touch function is improved, and the polydimethylsiloxane chain link has the advantages of improving the adsorption capacity of the polymer, improving the touch function and the likeThe polymer has no hydrophilicity, no thermal yellowing and no phenol yellowing.
② introduction of polyether and polyether modified amido of third generation silicone oil, compared with second generation amido silicone oil, the touch function is not improved, but is reduced, the hydrophilicity of polydimethylsiloxane is only increased, the main reason is that the molecular weight of the third generation silicone oil is very small, the whole molecular weight is about 5000-20000, and the chain link of the polydimethylsiloxane is smallThe molecular weight of the polydimethylsiloxane is about 370-7000, and the film forming property of the polydimethylsiloxane chain link is damaged due to the introduction of polyether. Polydimethylsiloxane chain link in inverse amino silicone oilThe molecular weight of the (B) is about 5000-40000, and the film forming property of the (B) is not interfered. The introduction of the third generation silicone oil polyether or polyether modified amino group contributes to fluffy touch.
③ the polydimethylsiloxane chain of the fourth generation silicone oil is an independently synthesized active monomer, namely α, omega-epoxypropyl oxypropyl polydimethylsiloxane, the structural formula of which is:
whereinThe molecular weight of the polydimethylsiloxane chain link can be about 15000 by an acid equilibrium catalysis method, and can be about 80000 by an alkali equilibrium catalysis method invented by the company, and the molecular weight of the polydimethylsiloxane chain link can be equivalent to that of amino silicone oil.
The amino polyether of the fourth generation silicone oil is linearly connected with α omega-epoxypropyl oxypropyl polydimethylsiloxane, the amino polyether has little influence on the film forming of polydimethylsiloxane chain links after linear connection, under the theory of directional adsorption of amino cation, under most conditions, the amino polyether has no influence on the film forming of polydimethylsiloxane chain links but helps to be larger, so in the experimental data of the first generation silicone oil and the second generation silicone oil, the finishing effect of the fourth generation silicone oil is better than that of the second generation amino silicone oil, and the amino polyether is the best evidence.
Wherein R1 ═ CH3，-C2H5，-C4H9,-H；a＝1～20,b＝1～40.
The amino polyether introduced into the fourth generation silicone oil is known from the experimental data in the table I and the table II, and has great contribution to fluffy touch and little contribution to softness and smoothness. The tactile contribution of fourth generation silicone oils is mainly due to the polydimethylsiloxane chain. Thus, its "oily" feel is still unsolved.
④ from the first to fourth generation of silicone oils we conclude that the current textile silicone materials have a 90% -99% contribution to the tactile style from the polydimethylsiloxane segments, and therefore have a significant "oiliness" from the first to fourth generation of silicone oils.
Along with the increasing living standard of people, the touch requirement of the fabric on the market returns to natural and natural touch. Therefore, the oiliness touch characteristics of the fabric finished by the organosilicon material are very outstanding, and the close-fitting clothing is lack of comfort.
Therefore, a new hand feeling finishing agent is needed to solve the technical problem that the finished fabric has obvious oily touch feeling.
Disclosure of Invention
The invention aims to provide a polyquaternary ammonium base glucose polydimethylsiloxane polyether, a preparation method thereof and a hand feeling finishing agent using the polyquaternary ammonium base glucose polydimethylsiloxane polyether. In the polyquaternary ammonium group glucose polydimethylsiloxane polyether and the hand feeling finishing agent thereof, glucose methylamine is introduced into a polydimethylsiloxane chain link, so that the touch style of a high polymer is greatly changed. The method comprises the following steps that firstly, at normal temperature, five hydroxyl groups of the glucose methylamine have strong independent film forming capability, and a film formed by the glucose methylamine is a solid film, so that the volume of yarns can be increased, the fabric has obvious fluffy feeling, and the fluffy feeling of the fabric is completely different from that of polydimethylsiloxane of a liquid polymer; the solid film formed by the glucose methylamine is dry, smooth in silk quality, fine, soft and skin-friendly, natural in smoothness and absolutely not sticky, and is greatly different from the smoothness provided by the polydimethylsiloxane chain link with large molecular weight.
In addition, the invention provides proper intramolecular softness for the polyquaternary ammonium group glucose siloxane polyether by utilizing the polydimethylsiloxane chain link with small molecular weight, reduces intramolecular rigidity so as to meet proper wearability and also provides certain touch softness.
In order to achieve the above object, the present invention provides a poly quaternary ammonium glucose polydimethylsiloxane polyether represented by the following general formula I:
wherein A is-Selected from Cl-，Br-，I-，CH3COO-，C2H5COO-，C3H7COO-Or one of laurate radical; n is an integer selected from 10 to 1000; a is an integer selected from 1 to 20; m is an integer selected from 2 to 100.
The invention also provides a preparation method of the poly quaternary ammonium base glucose polydimethylsiloxane polyether, which comprises the following steps:
step 1,1,3, 3-tetramethyl dihydro disiloxane and allyl glycidyl ether are used as starting materials, an isopropanol solution of chloroplatinic acid is used as a catalyst, and the reaction is carried out at the temperature of 70-80 ℃ to obtain 1, 3-epoxypropyl oxypropyl disiloxane;
step 2, taking the 1, 3-epoxypropyloxypropyl disiloxane and the octamethylcyclotetrasiloxane obtained in the step 1 as starting materials, taking tetramethylammonium hydroxide as a catalyst, and reacting at 80-155 ℃ under the protection of nitrogen to obtain α omega-epoxypropyloxypropyl polydimethylsiloxane;
step 3, reacting α, omega-epoxypropyloxypropylpolydimethylsiloxane obtained in the step 2 and glucose methylamine serving as starting materials at the temperature of 60-85 ℃ in the presence of isopropanol to obtain α, omega-methylamino glucose isopropyl hydroxypropyloxypropylpolydimethylsiloxane;
and 4, adding acid into the α omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane obtained in the step 3, then adding α omega-epoxy propyl polyether, and reacting at the temperature of 60-85 ℃ in the presence of isopropanol to obtain the target product, namely the quaternary ammonium group glucose polydimethylsiloxane polyether.
In an embodiment of the present invention, in the step 1, the molar ratio of the 1,1,3, 3-tetramethyldihydrodisiloxane to the allyl glycidyl ether is in the range of 1 (2.1-4.0); the adding amount of the catalyst is 0.05-0.1% of the total mass of the reaction system in the step 1; and the mass percentage concentration of the isopropanol solution of chloroplatinic acid as the catalyst is 1%.
In one embodiment of the invention, in the step 2, the mass ratio of the 1, 3-epoxypropyloxypropyldisiloxane to the octamethylcyclotetrasiloxane is in the range of (34-90): 1000; the adding amount of the tetramethylammonium hydroxide is 0.05-0.1 percent of the total mass of the reaction system in the step 2.
In an embodiment of the invention, in the step 3, the molar ratio of the α, omega-epoxypropyloxypropyl polydimethylsiloxane to the glucose methylamine is in the range of 1.0 (2.0-2.2), and the addition amount of the isopropanol is 40% -70% of the total mass of the reaction system in the step 3.
In one embodiment of the invention, in the step 4, the molar ratio of the α, omega-methylamino glucose, isopropyl alcohol, hydroxypropyl oxide, polydimethylsiloxane and α, omega-epoxy propyl polyether is (0.5-2): 1, the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4, the addition amount of the acid is equal to the molar mass of the α, omega-epoxy propyl polyether, the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4, and preferably, the acid is selected from HCl, HBr, HI and CH3COOH、CH3CH2COOH、CH3C2H4COOH or lauric acid.
In a preferred embodiment of the present invention, a method for preparing the above poly quaternary ammonium glucose polydimethylsiloxane polyether is provided, which comprises the following steps:
step 1, taking 1,1,3, 3-tetramethyl dihydro disiloxane and allyl glycidyl ether as starting materials, mixing the 1,1,3, 3-tetramethyl dihydro disiloxane and the allyl glycidyl ether according to the molar ratio of 1 (2.1-4.0), taking an isopropanol solution of chloroplatinic acid with the mass percentage concentration of 1% as a catalyst, and reacting at 70-80 ℃ to obtain 1, 3-epoxypropyloxypropyl disiloxane;
step 2, taking the 1, 3-epoxypropyloxydropyldisiloxane and the octamethylcyclotetrasiloxane obtained in the step 1 as starting materials, taking tetramethylammonium hydroxide as a catalyst, and reacting at 80-155 ℃ under the protection of nitrogen to obtain α omega-epoxypropyloxydropylpolydimethylsiloxane, wherein the mass ratio of the 1, 3-epoxypropyloxydropyldisiloxane to the octamethylcyclotetrasiloxane is (34-90): 1000, and the adding amount of the tetramethylammonium hydroxide is 0.05-0.1% of the total mass of the reaction system in the step 2;
step 3, using α, omega-epoxypropyloxypropyl polydimethylsiloxane obtained in the step 2 and glucose methylamine as starting materials, and reacting at the temperature of 60-85 ℃ in the presence of isopropanol to obtain α, omega-methylamino glucose isopropyl hydroxy propyl oxypropyl polydimethylsiloxane, wherein the molar ratio of the α, omega-epoxypropyloxypropyl polydimethylsiloxane to the glucose methylamine is within the range of 1.0 (2.0-2.2), and the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 3;
and 4, adding acid into the α omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane obtained in the step 3, then adding α omega-epoxypropyl polyether, reacting at the temperature of 60-85 ℃ in the presence of isopropanol, and obtaining the target product namely the quaternary ammonium group glucose polydimethylsiloxane polyether, wherein the molar ratio of the α omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane to the α omega-epoxypropyl polyether is (0.5-2): 1, the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4, the addition amount of the acid is equal to the molar mass of the α omega-epoxypropyl polyether, and the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4.
In a preferred embodiment of the invention, the acid is selected from HCl, HBr, HI, CH3COOH、CH3CH2COOH、CH3C2H4COOH or lauric acid.
In an embodiment of the present invention, the above steps 1 to 4 further include a step of removing unreacted reactant and a step of removing isopropanol, for example, the step 1 further includes: removing unreacted allyl glycidyl ether under the conditions of vacuum degree of-0.1 to-0.095 Mpa and temperature of 140 to 180 ℃; the step 2 further comprises: removing unreacted octamethylcyclotetrasiloxane and the like under the conditions that the vacuum degree is-0.1 to-0.095 Mpa and the temperature is 140 to 160 ℃; and, the step 4 further comprises: and (3) distilling the isopropanol at 85-120 ℃.
In an embodiment of the present invention, the reaction time in the step 1 is 4 to 12 hours; in the step 2, the reaction is carried out for 8 to 48 hours at the temperature of 80 to 110 ℃, and then the reaction is carried out for 2 to 5 hours at the temperature of 135 to 155 ℃; the reaction time of the step 3 is 12-48 hours; the reaction time of the step 4 is 12-60 hours.
Therefore, in a preferred embodiment of the present invention, a method for preparing the above poly quaternary ammonium glucose polydimethylsiloxane polyether is provided, the method comprises the following steps:
step 1, taking 1,1,3, 3-tetramethyl dihydro disiloxane and allyl glycidyl ether as starting materials, mixing the 1,1,3, 3-tetramethyl dihydro disiloxane and the allyl glycidyl ether according to the molar ratio of 1 (2.1-4.0), taking an isopropanol solution of chloroplatinic acid with the mass percentage concentration of 1% as a catalyst, reacting for 4-12 hours at 70-80 ℃, and removing unreacted allyl glycidyl ether under the conditions of vacuum degree of-0.1-0.095 Mpa and temperature of 140-180 ℃ to obtain 1, 3-epoxypropyloxypropyl disiloxane;
step 2, taking the 1, 3-epoxypropyloxypropyldisiloxane and the octamethylcyclotetrasiloxane obtained in the step 1 as starting materials, taking tetramethylammonium hydroxide as a catalyst, reacting for 8-48 hours at 80-110 ℃ under the protection of nitrogen, then, reacting for 2-5 hours at 135-155 ℃, and removing unreacted octamethylcyclotetrasiloxane and similar substances thereof under the conditions of vacuum degree of-0.1-0.095 Mpa and temperature of 140-160 ℃ to obtain α omega-epoxypropyloxypropylpolydimethylsiloxane, wherein the mass ratio of the 1, 3-epoxypropyldisiloxane to the octamethylcyclotetrasiloxane ranges from (34-90) to 1000, and the adding amount of the tetramethylammonium hydroxide is 0.05-0.1% of the total mass of the reaction system in the step 2;
step 3, reacting α omega-epoxypropyloxypropylpolydimethylsiloxane and glucose methylamine obtained in the step 2 as starting materials at the temperature of 60-85 ℃ for 12-48 hours in the presence of isopropanol to obtain α omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane, wherein the molar ratio of the α omega-epoxypropyloxypropyl polydimethylsiloxane to the glucose methylamine is 1.0 (2.0-2.2), and the adding amount of the isopropanol is 40% -70% of the total mass of the reaction system in the step 3;
and 4, adding acid into the α omega-methylamino glucose isopropyl oxide dimethyl silicone polymer obtained in the step 3, then adding α omega-epoxy propyl polyether, reacting for 12-60 hours at 60-85 ℃ in the presence of isopropanol, and distilling the isopropanol at 80-120 ℃ to obtain a target product, namely the quaternary ammonium base glucose dimethyl silicone polymer polyether, wherein the molar ratio of the α omega-methylamino glucose isopropyl oxide propyl dimethyl silicone polymer to the α omega-epoxy propyl polyether is (0.5-2): 1, the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4, the addition amount of the acid is equal to the molar mass of the α omega-epoxy propyl polyether, and the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4.
The invention also provides a hand feeling finishing agent, the effective component of the hand feeling finishing agent is the poly quaternary ammonium group glucose polydimethylsiloxane polyether in claim 1.
In one embodiment of the present invention, the hand feeling finishing agent comprises, by mass: 30-40% of the poly quaternary ammonium group glucose polydimethylsiloxane polyether; 68-46% of a nonionic emulsifier; 0.01-0.05% acetic acid; the balance of water; and the pH value range of the hand feeling finishing agent is 4.5-6.5.
In an embodiment of the present invention, the nonionic emulsifier is an isomeric alcohol polyoxyethylene ether represented by the following general formula: CH (CH)3(CHCH3)a(CH2)bO(C2H4O)cH represents; wherein a is 1-4, b is 1-10, and c is 3-20. Preferably, the nonionic emulsifier is one or a mixture of several of isomeric C8 alcohol polyoxyethylene ether, isomeric C10 alcohol polyoxyethylene ether or isomeric C13 alcohol polyoxyethylene ether.
In the polyquaternary ammonium group glucose polydimethylsiloxane polyether and the hand feeling finishing agent thereof, glucose methylamine is introduced into a polydimethylsiloxane chain link, so that the touch style of a high polymer is greatly changed. Firstly, the five hydroxyl groups of the glucose methylamine have strong independent film forming capability at normal temperature, the film formed by the glucose methylamine is a solid film, the volume of the yarn can be increased, the fabric has obvious fluffy feeling, and the film is in contact with polydimethylsiloxane of a liquid polymerThe fluffy feeling provided by the formed film is completely different; the solid film formed by the glucose methylamine is dry, smooth in silk quality, fine, soft and skin-friendly, natural in smoothness and absolutely not sticky, and is greatly different from the smoothness provided by the polydimethylsiloxane chain link with large molecular weight.
In addition, the invention provides proper intramolecular softness for the polyquaternary ammonium group glucose siloxane polyether by utilizing the polydimethylsiloxane chain link with small molecular weight, reduces intramolecular rigidity so as to meet proper wearability and also provides certain touch softness.
In the invention, the film-forming appearance state of the hand feeling finishing agent is changed from a liquid state or a semi-colloidal state in the prior art to a solid state or an elastomer solid state through a synthesis process line and an initial material selection, so that the technical problems that after the finishing of the traditional organic silicon emulsion, the fabric feels oily too heavy to touch, so that the fabric is not natural and uncomfortable to be stuck to hands and is close to the skin are thoroughly solved. Therefore, the hand feeling finishing agent of the invention endows the fabric with new touch feeling again: the cotton fiber fabric is dry, non-sticky, dry, natural, fine, smooth and skin-friendly, silky, and has beneficial functions of instant hydrophilicity, no thermal yellowing, no phenol yellowing and the like. The product of the invention improves the added value of the fabric. The product of the invention realizes large-scale industrialized production.
Detailed Description
Hereinafter, the technique of the present invention will be described in detail with reference to specific embodiments. It should be understood that the following detailed description is only for the purpose of assisting those skilled in the art in understanding the present invention, and is not intended to limit the present invention.
Example 1A Polyquaternary ammonium group glucose polydimethylsiloxane polyether
In this example, a polyquaternary ammonium based glucose polydimethylsiloxane polyether is provided. The poly quaternary ammonium glucose polydimethylsiloxane polyether is represented by the following general formula I:
wherein A is-Selected from Cl-，Br-，I-，CH3COO-，C2H5COO-，C3H7COO-Or one of laurate radical; n is an integer selected from 10 to 1000; a is an integer selected from 1 to 20; m is an integer selected from 2 to 100.
The preparation method of the poly quaternary ammonium group glucose polydimethylsiloxane polyether comprises the following specific steps:
step 1, taking 1,1,3, 3-tetramethyl dihydro disiloxane and allyl glycidyl ether as starting materials, mixing the 1,1,3, 3-tetramethyl dihydro disiloxane and the allyl glycidyl ether according to a molar ratio of 1 (2.1-4.0), taking an isopropanol solution of chloroplatinic acid with the mass percentage concentration of 1% as a catalyst, wherein the used amount of the catalyst is 0.05-0.1% of the total weight of a reaction system, adding the catalyst in batches at the temperature of 45-85 ℃, reacting for 4-12 hours at the temperature of 70-80 ℃, removing unreacted allyl glycidyl ether under the conditions of the vacuum degree of-0.1-0.095 Mpa and the temperature of 140-180 ℃ after detecting SiH characteristic peak by infrared chromatography, and obtaining 1, 3-epoxypropyloxypropyl disiloxane;
the above reaction equation is:
step 2, taking the 1, 3-epoxypropyloxypropyldisiloxane and the octamethylcyclotetrasiloxane obtained in the step 1 as starting materials, taking tetramethylammonium hydroxide as a catalyst, reacting for 8-48 hours at 80-110 ℃ under the protection of nitrogen, then, reacting for 2-5 hours at 135-155 ℃, and removing unreacted octamethylcyclotetrasiloxane and similar substances thereof under the conditions of vacuum degree of-0.1-0.095 Mpa and temperature of 140-160 ℃ to obtain α omega-epoxypropyloxypropylpolydimethylsiloxane, wherein the mass ratio of the 1, 3-epoxypropyldisiloxane to the octamethylcyclotetrasiloxane ranges from (34-90) to 1000, and the adding amount of the tetramethylammonium hydroxide is 0.05-0.1% of the total mass of the reaction system in the step 2;
the obtained α, omega-epoxypropyloxypropylpolydimethylsiloxane had the following structure:
wherein m 10 c1000；
The above reaction equation is:
step 3, reacting α omega-epoxypropyloxypropylpolydimethylsiloxane and glucose methylamine obtained in the step 2 as starting materials at the temperature of 60-85 ℃ for 12-48 hours in the presence of isopropanol to obtain α omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane, wherein the molar ratio of the α omega-epoxypropyloxypropyl polydimethylsiloxane to the glucose methylamine is 1.0 (2.0-2.2), and the adding amount of the isopropanol is 40% -70% of the total mass of the reaction system in the step 3;
the structure of the glucosylmethylamine is as follows:
the above reaction equation is:
wherein n is 10-1000; and the number of the first and second groups,
step 4, adding acid into the α omega-methylamino glucose isopropyl oxide dimethyl silicone polymer obtained in the step 3, then adding α omega-epoxy propyl polyether, reacting for 12-60 hours at 60-85 ℃ in the presence of isopropanol, and distilling out the isopropanol at 80-120 ℃ to obtain a target product, namely the quaternary ammonium base glucose dimethyl silicone polymer polyether, wherein the molar ratio of α omega-methylamino glucose isopropyl oxide propyl dimethyl silicone polymer to α omega-epoxy propyl polyether is (0.5-2): 1, the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4, the addition amount of the acid is equal to the molar mass of α omega-epoxy propyl polyether, and the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4;
wherein the α, omega-epoxypropyl polyether has the following structure:
wherein a is 1-20, and b is 1-60;
the above reaction equation is:
wherein A is-＝Cl-、Br-、I-、CH3COO-、C2H5COO-、C3H7COO-Or one of cinnamate radical; and n is 10 to 1000, a is 1 to 20, b is 1 to 60, and m is 2 to 100.
Example 2A hand feel finish
In this embodiment, there is provided a hand finish comprising, in mass percent: 30-40% of the quaternary ammonium glucosyldimethicone polyether prepared in example 1; 68-46% of a nonionic emulsifier; 0.01-0.05% acetic acid; the balance of water; and the pH value range of the hand feeling finishing agent is 4.5-6.5.
The nonionic emulsifier is isomeric alcohol polyoxyethylene ether and is represented by the following general formula: CH (CH)3(CHCH3)a(CH2)bO(C2H4O)cH represents; wherein a is 1 to 4,b is 1 to 10, and c is 3 to 20. Preferably, the nonionic emulsifier is one or a mixture of several of isomeric C8 alcohol polyoxyethylene ether, isomeric C10 alcohol polyoxyethylene ether or isomeric C13 alcohol polyoxyethylene ether.
The preparation method of the hand feeling finishing agent is specifically as follows.
Uniformly mixing the polyquaternary ammonium glucose polydimethylsiloxane polyether obtained in the embodiment 1 with the non-ionic emulsifier, slowly adding water for dilution, and finally adjusting the pH value with acetic acid to ensure that the pH value of the finally obtained hand feeling finishing agent is between 4.5 and 6.5.
Example 3 Performance testing of the hand finish described in example 2
In this example, the film-forming properties of the hand finish obtained in example 2 were investigated.
The applicant finds that the touch styles of 'dry, natural, fine and smooth skin and silky texture' mainly come from the following aspects: the glucose methylamine chain links are introduced into the molecular structure of the polymer, the glucose methylamine has strong independent film forming capability at normal temperature, and in the high polymer polyquaternary ammonium group glucose isopropyl hydroxypropyl oxypropyl polydimethylsiloxane polyether molecules, two adjacent polyquaternary ammonium group glucose chain links form a very ordered and compact solid film with a very smooth surface after high-temperature dehydration, and the touch smoothness is very unique.
Thus, in this example, the final film-forming properties of different types of silicone oils were first investigated by observing films made by baking (temperature 105 ℃ C. -110 ℃ C., baking 2-3 hours) the product emulsion on a glass petri dish.
The experimental conditions are specifically as follows: glass surface ware, diameter 8cm, oven temperature 105-110 deg.C, time 2.5 hours, emulsion solid content about 45%, baking emulsion weight: 5g of the total weight. The results are shown in Table 1.
TABLE 1 comparison of the Properties of the second, fourth and inventive hand finishes
In addition, the applicant also takes 32s and 40s spandex-containing silk fine cotton-carding knitted fabrics as experimental objects, the solid content of an emulsion product is 45%, the using amount is 80g/l, the rolling residual rate is 80%, the setting temperature is 190 ℃, the vehicle speed is 40m/min, the retention time is 40 seconds, the fabric is fully remoistened for 2 hours after setting, the hydrophilicity and the hand feeling evaluation of the fabric samples after the second generation, the fourth generation and the hand feeling finishing agent are tested, the yellowing resistance and the phenol yellowing resistance are tested, and the data in tables 2 to 4 are obtained.
Table 2 bulk contrast of cloth sample after second generation, fourth generation and finishing with the hand feeling finishing agent of the invention
Table 3 comparison of softness of cloth samples finished by the second generation, fourth generation and the hand feeling finishing agent of the invention
TABLE 4 smoothness comparison of cloth samples finished with second generation, fourth generation and the hand feeling finishing agent of the present invention
And (4) conclusion: from the experimental results of the above tables 1 to 4, it can be obtained:
A. the film made of amino silicone oil is a liquid or semi-liquid oily film, the finished fabric has heavy oil smoothness, and when the using amount is large, the fabric has obvious 'sticky hand' feeling, and the comfort of underwear is not enough.
B. The film formed by the amino polyether block silicone oil is a liquid or semi-liquid film, and the oiliness of the fabric finished by the film is slightly lighter than that of the amino silicone oil. When the dosage is larger, the hand-sticking feeling is obvious, and the comfort of close-fitting clothes is also deficient.
C. The film formed by the polymer emulsion is a solid, semi-solid, smooth and elastic film, and the fabric finished by the film is smooth, dry, non-sticky, fine and smooth in touch and more natural and comfortable to wear next to skin. The material of the invention is a beneficial supplement of modified organosilicon material.
D. Experiments I and II show that the material has dry, natural, fine and smooth skin-friendly and silky touch style touch function, and the main reason is that a special chain link capable of changing the film forming state of a polysiloxane chain link is introduced into a monomolecular structure. The poly quaternary ammonium group glucose chain link changes polysiloxane which is still liquid at ultralow temperature of-38 ℃ into solid at normal temperature, thereby fundamentally solving the problem of 'sticky touch' of the polysiloxane.
E. Due to the super strong film forming capability of the poly-quaternary ammonium glucose and the unique characteristics of the formed film, compact, smooth, mellow, dry and comfortable touch feeling and the like, the 'oily' characteristic of the polysiloxane is changed.
F. Since the polymer of the present invention is solid or semi-solid after film formation, its ability to swell yarns is more prominent than the fluffy feel of liquid/semi-liquid polymers.
G. From the experimental contents of the technical background table two, it is known that: first generation silicone oilsThe hydroxyl silicone oil and the methyl silicone oil have no thermal yellowing and phenol yellowing, and the molecular structure of the second generation amino silicone oil introduces primary amino (-NH)2) Secondary amino (-NRH) causes thermal yellowing and phenol yellowing; in the third generation silicone oil, the polyether silicone oil is different from polyether modified amino silicone oil, and the polyether silicone oil is free of thermal yellowing and phenol yellowing, so that instant hydrophilic performance is obtained; the polyether modified amino silicone oil produces thermal yellowing and phenol yellowing due to the introduction of secondary amino (-NHR), and the obtained hydrophilicity is general-grade hydrophilicity and is not instant hydrophilicity; comprises a fourth generation silicone oil amino polyether block, and introduces primary amino (-NH)2) The secondary amino group (-NRH) also causes thermal yellowing and phenol yellowing in the experimental results. The tertiary amine group is introduced, but the reaction result of the process is completely converted into the quaternary ammonium group, so that the polymer of the invention has no thermal yellowing and phenol yellowing.
H. And (4) conclusion: quaternary ammonium group does not generate thermal yellowing and phenol yellowing, and primary amino (-NH)2) Secondary amino (-NRH) causes thermal yellowing and phenol yellowing.
I. The invention introduces reactive highly hydrophilic α, omega-epoxypropyl polyether, and the chemical structure is as follows:
the hydrophilicity of the product can be adjusted by adjusting the parameter b and the molecular weight of the polyether.
In addition, applicants have found that in the present invention, the structure of the α, omega-epoxypropyloxypropyl polydimethylsiloxane obtained in step 2 will result in properties in the final product α, omega-epoxypropyloxypropyl polydimethylsiloxane is as follows:
wherein,
when n is more than or equal to 40 and less than or equal to 60, the terminal target product is biased to be fluffy; when n is more than or equal to 60 and less than or equal to 80, the terminal target product is biased to be soft; when n is more than or equal to 80 and less than or equal to 130, the terminal target product is biased to be smooth.
Application example 1 bulky product
In this example, a hand feeling finishing agent, a fluffy product, was provided, and the specific preparation method thereof was as follows.
In the step (1), a chloroplatinic acid isopropanol solution with the concentration of 1% is used as a catalyst, 1,3, 3-tetramethyl dihydrodisiloxane and allyl glycidyl ether (wherein the molar ratio of the two is 1: 2.1-4.0) are added in batches at the temperature of 45-85 ℃, the temperature is kept at 70-80 ℃, the temperature is kept for 4-12 hours, after the disappearance of an SiH characteristic peak detected by infrared chromatography, unreacted allyl glycidyl ether is removed at the vacuum degree of-0.1-0.095 Mpa and the temperature of 140-180 ℃ to obtain a product.
1, 3-epoxypropyldisiloxaneThe amount of the chloroplatinic acid catalyst is 0.05-0.1 percent of the weight of the system, and the molar ratio of 1,1,3, 3-tetramethyl dihydrodisiloxane to allyl glycidyl ether is as follows: 1: 2.1-4.0. The above reaction equation is:
adding tetramethylammonium hydroxide serving as a catalyst into a mixture of the 1, 3-epoxypropyloxypropyl disiloxane and octamethylcyclotetrasiloxane obtained in the step (1), preserving heat for 8-48 hours at the temperature of 80-110 ℃, heating to 135-155 ℃ under the protection of nitrogen, preserving heat for 2-5 hours, and removing unreacted octamethylcyclotetrasiloxane and the like at the vacuum degree of-0.1-0.095 Mpa and the temperature of 140-160 ℃ to obtain α, omega-epoxypropyloxypropyl polydimethylsiloxane, wherein the structure is as follows:
wherein m is 50, and the amount of the tetramethylammonium hydroxide is 0.1-0.05% of the weight of the system; the weight ratio of the 1, 3-epoxypropyl oxypropyl disiloxane to the octamethylcyclotetrasiloxane is as follows: 90:1000. The above reaction equation is:
wherein m is 50
Step (3) adding the target product α, omega-epoxypropyloxypropylpolydimethylsiloxane obtained in step (2) into a mixture of glucose methylamine and isopropanol, wherein the structure of the glucose methylamine is as follows:
reacting for 12-48 hours at the temperature of 60-85 ℃ to obtain α, omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane, wherein the reaction equation is as follows:
wherein the isopropanol accounts for 40-70% of the total weight of the reaction system, and the molar ratio of the glucose methylamine to the α omega-epoxypropyloxypropyl polydimethylsiloxane is 2.0-2.2: 1.
Step (4) the purpose of step (3)Adding acid into α omega-methylamino glucose hydroxypropyl oxypropyl polydimethylsiloxane, mixing uniformly at 20-60 ℃, adding α omega-epoxy propyl polyether, reacting for 12-60 hours at 60-85 ℃, distilling off isopropanol at 85-120 ℃ to obtain the target product, namely the poly (quaternary ammonium) glucose hydroxypropyl oxypropyl polydimethylsiloxane polyether, wherein the acid is HCl, HBr, HI, CH3COOH，CH3CH2COOH，CH3C2H4COOH, lauric acid, the weight of which is equal to the molar amount of the glucose methylamine, wherein the α, omega-epoxypropyl polyether is characterized by the following structure:
wherein a is 2-6, and b is 15-40. The above reaction equation is as follows:
wherein A is-＝Cl-，Br-，I-，CH3COO-，C2H5COO-，C3H7COO-Laurate radical.
n＝50,a＝2～6,b＝15～40,m＝2～100。
The mole ratio of the α omega-methylamino glucose isopropyl oxide propyl polydimethylsiloxane to the α omega-epoxy propyl polyether is 2: 3-3: 4, wherein the isopropanol accounts for 40-70% of the total weight of the system.
And (5) uniformly mixing the target product poly quaternary ammonium glucose isopropyl hydroxypropyl oxide polydimethylsiloxane polyether in the step (4) with a nonionic emulsifier heterogeneous alcohol polyoxyethylene ether, slowly adding water for dilution, finally adjusting the pH value with acetic acid to be 4.5-6.5, and then obtaining the target product poly quaternary ammonium glucose isopropyl oxide polydimethylsiloxane polyether hand feeling finishing agent. The hand feeling finishing agent comprises the following components in percentage by mass: 40% of polyquaternary ammonium glucose polysiloxane polyether, 2.5% of deca-isomeric alcohol polyoxyethylene-5, 2.5% of deca-isomeric alcohol polyoxyethylene-9, 0.5% of acetic acid with the concentration of 100%, and the balance of water. Is marked as hand feeling finishing agent A.
Application example 2 Soft type product
In this example, a hand feeling finishing agent, which is a soft type product, was provided, and its specific preparation method is as follows.
Embodiment B (Soft type product)
In the step (1), a chloroplatinic acid isopropanol solution with the concentration of 1% is used as a catalyst, 1,3, 3-tetramethyl dihydrodisiloxane and allyl glycidyl ether (wherein the molar ratio of the two is 1: 2.1-4.0) are added in batches at the temperature of 45-85 ℃, the temperature is kept at 70-80 ℃, the temperature is kept for 4-12 hours, after the disappearance of an SiH characteristic peak detected by infrared chromatography, unreacted allyl glycidyl ether is removed at the vacuum degree of-0.1-0.095 Mpa and the temperature of 140-180 ℃ to obtain a product.
1, 3-epoxypropyldisiloxaneThe amount of the chloroplatinic acid catalyst is 0.05-0.1 percent of the weight of the system, and the molar ratio of 1,1,3, 3-tetramethyl dihydrodisiloxane to allyl glycidyl ether is as follows: 1: 2.1-4.0. The above reaction equation is:
adding tetramethylammonium hydroxide serving as a catalyst into a mixture of the 1, 3-epoxypropyloxypropyl disiloxane and octamethylcyclotetrasiloxane obtained in the step (1), preserving heat for 8-48 hours at the temperature of 80-110 ℃, heating to 135-155 ℃ under the protection of nitrogen, preserving heat for 2-5 hours, and removing unreacted octamethylcyclotetrasiloxane and the like at the vacuum degree of-0.1-0.095 Mpa and the temperature of 140-160 ℃ to obtain α, omega-epoxypropyloxypropyl polydimethylsiloxane, wherein the structure is as follows:
wherein m is 80, and the using amount of the tetramethylammonium hydroxide is 0.1-0.05% of the weight of the system; the weight ratio of the 1, 3-epoxypropyl oxypropyl disiloxane to the octamethylcyclotetrasiloxane is as follows: 55:1000. The above reaction equation is:
wherein m is 80
Step (3) adding the target product α, omega-epoxypropyloxypropylpolydimethylsiloxane obtained in step (2) into a mixture of glucose methylamine and isopropanol, wherein the structure of the glucose methylamine is as follows:
reacting for 12-48 hours at the temperature of 60-85 ℃ to obtain α, omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane, wherein the reaction equation is as follows:
wherein the isopropanol accounts for 40-70% of the total weight of the reaction system, and the molar ratio of the glucose methylamine to the α omega-epoxypropyloxypropyl polydimethylsiloxane is 2.0-2.2: 1.
Step (4) adding acid into the target product α, omega-methylamino glucose hydroxypropyl oxypropyl polydimethylsiloxane obtained in the step (3) at the temperature of 20-60 ℃, uniformly mixing, then adding α, omega-epoxy propyl polyether, reacting for 12-60 hours at the temperature of 60-85 ℃, and then distilling off isopropanol at the temperature of 85-120 ℃ to obtain the target product, namely the polyquaternary ammonium glucose hydroxypropyl oxypropyl polydimethylsiloxane polyether, wherein the acid is HCl, HBr, HI, CH3COOH，CH3CH2COOH，CH3C2H4COOH, lauric acid, the weight of which is equal to the molar amount of the glucose methylamine, wherein the α, omega-epoxypropyl polyether is characterized by the following structure:
wherein a is 2-6, b is 15-40
The above reaction equation is as follows:
wherein A is-＝Cl-，Br-，I-，CH3COO-，C2H5COO-，C3H7COO-Laurate radical.
n＝80,a＝2～6，b＝15～40,m＝2～100。
The mole ratio of the α omega-methylamino glucose isopropyl oxide propyl polydimethylsiloxane to the α omega-epoxy propyl polyether is 3: 4-4: 5, wherein the isopropanol accounts for 40-70% of the total weight of the system.
And (5) uniformly mixing the target product poly quaternary ammonium glucose isopropyl hydroxypropyl oxide polydimethylsiloxane polyether in the step (4) with a nonionic emulsifier heterogeneous alcohol polyoxyethylene ether, slowly adding water for dilution, finally adjusting the pH value with acetic acid to be 4.5-6.5, and then obtaining the target product poly quaternary ammonium glucose isopropyl oxide polydimethylsiloxane polyether hand feeling finishing agent. The hand feeling finishing agent comprises the following components in percentage by mass: 40% of polyquaternary ammonium glucose polysiloxane polyether, 2.5% of deca-isomeric alcohol polyoxyethylene-5, 2.5% of deca-isomeric alcohol polyoxyethylene-9, 0.5% of acetic acid with the concentration of 100%, and the balance of water. Is marked as hand feeling finishing agent B.
Application example 3 smooth type product
In this example, a hand finish is provided, which is a smooth product, and is prepared as follows.
In the step (1), a chloroplatinic acid isopropanol solution with the concentration of 1% is used as a catalyst, 1,3, 3-tetramethyl dihydrodisiloxane and allyl glycidyl ether (wherein the molar ratio of the two is 1: 2.1-4.0) are added in batches at the temperature of 45-85 ℃, the temperature is kept at 70-80 ℃, the temperature is kept for 4-12 hours, after the disappearance of an SiH characteristic peak detected by infrared chromatography, unreacted allyl glycidyl ether is removed at the vacuum degree of-0.1-0.095 Mpa and the temperature of 140-180 ℃ to obtain a product.
1, 3-epoxypropyldisiloxaneThe dosage of the chloroplatinic acid catalyst is 0.05 to 0.1 percent of the weight of the system,the molar ratio of 1,1,3, 3-tetramethyldihydrodisiloxane to allyl glycidyl ether was: 1: 2.1-4.0. The above reaction equation is:
adding tetramethylammonium hydroxide serving as a catalyst into a mixture of the 1, 3-epoxypropyloxypropyl disiloxane and octamethylcyclotetrasiloxane obtained in the step (1), preserving heat for 8-48 hours at the temperature of 80-110 ℃, heating to 135-155 ℃ under the protection of nitrogen, preserving heat for 2-5 hours, and removing unreacted octamethylcyclotetrasiloxane and the like at the vacuum degree of-0.1-0.095 Mpa and the temperature of 140-160 ℃ to obtain α, omega-epoxypropyloxypropyl polydimethylsiloxane, wherein the structure is as follows:
wherein m is 130, and the amount of the tetramethylammonium hydroxide is 0.1-0.05% of the weight of the system; the weight ratio of the 1, 3-epoxypropyl oxypropyl disiloxane to the octamethylcyclotetrasiloxane is as follows: 34:1000. The above reaction equation is:
wherein m is 130
Step (3) adding the target product α, omega-epoxypropyloxypropylpolydimethylsiloxane obtained in step (2) into a mixture of glucose methylamine and isopropanol, wherein the structure of the glucose methylamine is as follows:
reacting for 12-48 hours at the temperature of 60-85 ℃ to obtain α, omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane, wherein the reaction equation is as follows:
wherein the isopropanol accounts for 40-70% of the total weight of the reaction system, and the molar ratio of the glucose methylamine to the α omega-epoxypropyloxypropyl polydimethylsiloxane is 2.0-2.2: 1.
Step (4) adding acid into the target product α, omega-methylamino glucose hydroxypropyl oxypropyl polydimethylsiloxane obtained in the step (3) at the temperature of 20-60 ℃, uniformly mixing, then adding α, omega-epoxy propyl polyether, reacting for 12-60 hours at the temperature of 60-85 ℃, and then distilling off isopropanol at the temperature of 85-120 ℃ to obtain the target product, namely the polyquaternary ammonium glucose hydroxypropyl oxypropyl polydimethylsiloxane polyether, wherein the acid is HCl, HBr, HI, CH3COOH，CH3CH2COOH，CH3C2H4COOH, lauric acid or a mixture of several of them, the weight of the added glucose methylamine is equal molar quantity, wherein the α, omega-epoxypropyl polyether has the structure:a is 2-6, and b is 15-40. The above reaction equation is as follows:
wherein A is-＝Cl-，Br-，I-，CH3COO-，C2H5COO-，C3H7COO-Lauric acid radical
n＝130,a＝2～6，b＝15～40,m＝2～100。
The mole ratio of the α omega-methylamino glucose isopropyl oxide propyl polydimethylsiloxane to the α omega-epoxy propyl polyether is 7: 6-8: 7, wherein the isopropanol accounts for 40-70% of the total weight of the system.
And (5) uniformly mixing the target product poly quaternary ammonium glucose isopropyl hydroxypropyl oxide polydimethylsiloxane polyether in the step (4) with a nonionic emulsifier heterogeneous alcohol polyoxyethylene ether, slowly adding water for dilution, finally adjusting the pH value with acetic acid to be 4.5-6.5, and then obtaining the target product poly quaternary ammonium glucose isopropyl oxide polydimethylsiloxane polyether hand feeling finishing agent. The hand feeling finishing agent comprises the following components in percentage by mass: 40% of polyquaternary ammonium glucose polysiloxane polyether, 2.5% of deca-isomeric alcohol polyoxyethylene-5, 2.5% of deca-isomeric alcohol polyoxyethylene-9, 0.5% of acetic acid with the concentration of 100%, and the balance of water. Is marked as hand feeling finishing agent C.
Performance evaluation examples
In this example, the properties of the hand finishes a to C were measured.
The final film forming properties were first examined. The experimental conditions are specifically as follows: glass surface ware, diameter 8cm, oven temperature 105-110 deg.C, time 2.5 hours, emulsion solid content about 45%, baking emulsion weight: 5g of the total weight. The results are reported in Table 5.
TABLE 5 film-forming properties of the hand finishes A to C of the invention.
In addition, the applicant also takes 32s and 40s spandex-containing silk fine cotton-carding knitted fabrics as experimental objects, the solid content of an emulsion product is 45%, the using amount is 80g/l, the rolling residual rate is 80%, the setting temperature is 190 ℃, the vehicle speed is 40m/min, the retention time is 40 seconds, the fabric is fully remoistened for 2 hours after setting, the hydrophilicity and the hand feeling evaluation of the fabric samples after the second generation, the fourth generation and the hand feeling finishing agent are tested, the yellowing resistance and the phenol yellowing resistance are tested, and the data in tables 6 to 8 are obtained.
Table 6 bulk contrast of cloth sample after second generation, fourth generation and finishing with hand feeling finishing agent A of the invention
Table 7 comparison of softness of cloth sample finished by the second generation, the fourth generation and the hand feeling finishing agent B
TABLE 8 smoothness comparison of cloth samples finished with second generation, fourth generation and inventive hand feeling finish C
The experimental data in tables 5 to 8 show that, in the present invention, the film-forming appearance state of the hand feeling finishing agent of the present invention is changed from the liquid state or semi-colloidal state in the prior art to the solid state or elastomer solid state through the selection of the synthesis process line and the starting material, thereby thoroughly changing the technical problem that the feeling of "oiliness" of the fabric is too heavy after the finishing of the prior organosilicon emulsion, so that the hand-sticking tight underwear is unnatural and uncomfortable. Therefore, the hand feeling finishing agent of the invention endows the fabric with new touch feeling again: the cotton fiber fabric is dry, non-sticky, dry, natural, fine, smooth and skin-friendly, silky, and has beneficial functions of instant hydrophilicity, no thermal yellowing, no phenol yellowing and the like. The product of the invention improves the added value of the fabric. The product of the invention realizes large-scale industrialized production.
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. It must be noted that the disclosed embodiments do not limit the scope of the invention. Rather, modifications and equivalent arrangements included within the spirit and scope of the claims are included within the scope of the invention.
Claims (11)
1. The poly quaternary ammonium glucose polydimethylsiloxane polyether is characterized by being represented by the following general formula I:
wherein A is-Selected from Cl-，Br-，I-，CH3COO-，C2H5COO-，C3H7COO-Or one of laurate radical; n is an integer selected from 10 to 1000; a is an integer selected from 1 to 20; b is 1-60; m is an integer selected from 2 to 100.
2. A process for the preparation of a polyquaternary ammonium based glucose polydimethylsiloxane polyether according to claim 1, characterized in that it comprises the following steps:
step 1,1,3, 3-tetramethyl dihydro disiloxane and allyl glycidyl ether are used as starting materials, an isopropanol solution of chloroplatinic acid is used as a catalyst, and the reaction is carried out at the temperature of 70-80 ℃ to obtain 1, 3-epoxypropyl oxypropyl disiloxane;
step 2, taking the 1, 3-epoxypropyloxypropyl disiloxane and the octamethylcyclotetrasiloxane obtained in the step 1 as starting materials, taking tetramethylammonium hydroxide as a catalyst, and reacting at 80-155 ℃ under the protection of nitrogen to obtain α omega-epoxypropyloxypropyl polydimethylsiloxane;
step 3, reacting α, omega-epoxypropyloxypropylpolydimethylsiloxane obtained in the step 2 and glucose methylamine serving as starting materials at the temperature of 60-85 ℃ in the presence of isopropanol to obtain α, omega-methylamino glucose isopropyl hydroxypropyloxypropylpolydimethylsiloxane;
and 4, adding acid into the α omega-methylamino glucose isopropyl oxypropyl polydimethylsiloxane obtained in the step 3, then adding α omega-epoxy propyl polyether, and reacting at the temperature of 60-85 ℃ in the presence of isopropanol to obtain the target product, namely the quaternary ammonium group glucose polydimethylsiloxane polyether.
3. The method according to claim 2, wherein in the step 1, the molar ratio of 1,1,3, 3-tetramethyldihydrodisiloxane to allyl glycidyl ether is in the range of 1 (2.1-4.0); the adding amount of the catalyst is 0.05-0.1% of the total mass of the reaction system in the step 1; and the mass percentage concentration of the isopropanol solution of chloroplatinic acid as the catalyst is 1%.
4. The method according to claim 2, wherein in the step 2, the mass ratio of the 1, 3-epoxypropyloxypropyldisiloxane to the octamethylcyclotetrasiloxane is in the range of (34-90): 1000; the adding amount of the tetramethylammonium hydroxide is 0.05-0.1 percent of the total mass of the reaction system in the step 2.
5. The preparation method according to claim 2, wherein in the step 3, the molar ratio of the α, omega-epoxypropyloxypropyl polydimethylsiloxane to the glucose methylamine is within a range from 1.0 (2.0) to 2.2, and the addition amount of the isopropanol is 40% to 70% of the total mass of the reaction system in the step 3.
6. The preparation method according to claim 2, wherein in the step 4, the molar ratio of the α, omega-methylamino glucose, i-hydroxypropyl oxypropyl polydimethylsiloxane to the α, omega-epoxypropyl polyether is (0.5-2): 1, the addition amount of the isopropanol is 40-70% of the total mass of the reaction system in the step 4, and the addition amount of the acid is equal to the molar mass of the α, omega-epoxypropyl polyether.
7. The method of claim 6, wherein the acid is selected from the group consisting of HCl, HBr, HI, CH3COOH、CH3CH2COOH、CH3C2H4COOH or lauric acid.
8. A hand feeling finishing agent characterized in that the active ingredient of the hand feeling finishing agent is the quaternary ammonium group glucose polydimethylsiloxane polyether of claim 1.
9. The hand finish of claim 8, wherein the hand finish comprises, in mass percent:
30-40% of poly quaternary ammonium glucose polydimethylsiloxane polyether;
68-46% of a nonionic emulsifier;
0.01-0.05% of acetic acid;
the balance of water; and the pH value range of the hand feeling finishing agent is 4.5-6.5.
10. The feel finish of claim 9 wherein said nonionic emulsifier is an isomeric alcohol polyoxyethylene ether.
11. The feel finish of claim 10, wherein the nonionic emulsifier is selected from the group consisting of polyoxyethylene ether of C8 isomeric alcohols, polyoxyethylene ether of C10 isomeric alcohols, and polyoxyethylene ether of C13 isomeric alcohols.
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| CN102558567A (en) * | 2011-12-10 | 2012-07-11 | 江阴市尼美达助剂有限公司 | Preparation method of quaternary copolymer block organic silicon oil |
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| CN102558567A (en) * | 2011-12-10 | 2012-07-11 | 江阴市尼美达助剂有限公司 | Preparation method of quaternary copolymer block organic silicon oil |
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