CN107501960B - Skin-feel hand feeling agent and preparation method thereof - Google Patents
Skin-feel hand feeling agent and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 229920002545 silicone oil Polymers 0.000 claims abstract description 44
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 21
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 18
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 18
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 13
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 7
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 7
- -1 (phenyl tert-butyl) methyldimethoxysilane Chemical compound 0.000 claims description 5
- COVFOTFXZVOYBR-UHFFFAOYSA-N N-[3-[dimethoxy(methyl)silyl]propyl]-N',N'-dimethylethane-1,2-diamine Chemical compound CN(CCNCCC[Si](OC)(OC)C)C COVFOTFXZVOYBR-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000004383 yellowing Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000010985 leather Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 239000000413 hydrolysate Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000011179 visual inspection Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 229920013822 aminosilicone Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- 244000256297 Euphorbia tirucalli Species 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- MONHWDVGWZHKAO-UHFFFAOYSA-N n'-[3-[dihydroxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound C[Si](O)(O)CCCNCCN MONHWDVGWZHKAO-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides a skin-feel hand feeling agent and a preparation method thereof. The skin-feel hand feel agent comprises: high molecular weight block silicone oil, a composite emulsifier, fumed silica and alkynol A04, wherein the weight ratio of the high molecular weight block silicone oil to the composite emulsifier to the fumed silica to the alkynol A04 is 65-75: 17-22: 3-6: 1-5, wherein the weight ratio of the composite emulsifier to the emulsifier is 1-3: 0.1-1.5: 0.1-1 parts of isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80, wherein the HLB value is 8-11, and the high molecular weight block silicone oil has a structural general formula shown in the following formula (I):
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a skin-feel hand feeling agent and a preparation method of the skin-feel hand feeling agent.
Background
The hand feeling is an important index for measuring the apparent quality of leather and woodware, and the traditional hand feeling agent cannot meet the crowd with high quality requirement along with diversification of the product requirement and higher requirement on the texture of the product.
The commonly used hand feeling agents include wax hand feeling agents and organic silicon hand feeling agents. The non-ionic hand feeling agent prepared by using wax as a raw material has oily hand feeling, strong plastic feeling and poor light and shadow effect.
One silicone hand disclosed in the prior art is a hand having silicone as a main component, which is usually obtained by ring-opening polymerization of octamethylcyclotetrasiloxane (D4) and modified silicone, and then emulsified.
Another organosilicon hand feeling agent disclosed in the prior art is a velvet organosilicon hand feeling agent, but only relates to a synthesis method and application of high molecular organosilicon, and the synthesis method comprises the steps of dehydrating and condensing two monomers, namely phenyldimethoxysilane and N- (β -aminoethyl) -gamma-aminopropyl methyl dihydroxy silane, and then carrying out equilibrium copolymerization on the two monomers and D4.
Disclosure of Invention
Through a large amount of researches, the inventor of the application finds that the molecular weight of the organosilicon component in the first organosilicon hand feeling agent is relatively small, and the organosilicon component is easy to migrate, so that the defect of non-durability is caused, and the D chain segment on the organosilicon main chain is randomly disturbed, so that the longer D chain segment is difficult to ensure, and the smooth hand feeling cannot be ensured. The hand feeling agent obtained by emulsifying simple macromolecular dimethyl silicone oil and hydroxyl silicone oil has dry and smooth hand feeling and is far away from skin feeling.
In addition, the dehydration polymerization of the organic silanol has the dual functions of anionic polymerization and gradual polymerization reaction mechanisms, the reaction temperature is strictly controlled, the silanol cohering gel is formed when the temperature is too high, and the molecular weight cannot meet the expected requirements when the temperature is too low.
The organosilicon in the second organosilicon hand feeling agent is polymerized randomly, the length of a D chain segment cannot be ensured, the reaction is violent and difficult to control, and a large amount of naked amino groups in a product are easy to yellow.
Accordingly, the present inventors have made specific efforts to overcome the disadvantages and shortcomings of the related art by finding out the above-mentioned problems.
A first aspect of the present invention relates to a skin feel hand treatment comprising: high molecular weight block silicone oil, a composite emulsifier, fumed silica and alkynol A04, wherein the weight ratio of the high molecular weight block silicone oil to the composite emulsifier to the fumed silica to the alkynol A04 is 65-75: 17-22: 3-6: 1-5, wherein the weight ratio of the composite emulsifier to the emulsifier is 1-3: 0.1-1.5: 0.1-1 parts of isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80, wherein the HLB value is 8-11, and the high molecular weight block silicone oil has a structural general formula shown in the following formula (I):
wherein x is 110-150, y is 15-30, and z is 20-40.
In the skin-touch feeling agent, the viscosity of the high molecular weight block silicone oil is 5000 to 20000 mPas.
In the skin-feel touch agent, the viscosity of the high-molecular-weight block silicone oil is 8000mPa & s to 10000mPa & s.
In the skin-feel hand feeling agent, the composite emulsifier is prepared from the following components in a weight ratio of 2: 1: 1, isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80.
In the skin-feel hand feeling agent, the weight ratio of the high molecular weight block silicone oil, the composite emulsifier, the fumed silica and the alkynol A04 is 72: 19: 5: 4.
in the above skin-feel hand feeling agent, the high molecular weight block silicone oil is prepared by a method comprising the steps of:
a. sequentially adding 90-98 parts of N- (β -dimethylaminoethyl) -gamma-aminopropylmethyldimethoxysilane, 2-5 parts of 7 mass percent sodium hydroxide aqueous solution and 0.3-0.5 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (II):
b. sequentially adding 95-99 parts of octamethylcyclotetrasiloxane and 1-3 parts of 7% (by mass) potassium hydroxide aqueous solution into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (III):
c. sequentially adding 90-98 parts of (phenyl tert-butyl) methyldimethoxysilane, 2-5 parts of 7 mass% of sodium hydroxide aqueous solution and 0.3-0.5 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (IV):
d. adding 30-38 parts of compound (II), 60-90 parts of compound (III), 15-20 parts of compound (IV) and 0.5-1 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, dehydrating and condensing at 110-120 ℃, and then adding 8-10 parts of trimethyl methoxy silane for end-capping degradation reaction to obtain the high molecular weight block silicone oil shown in formula (I).
In the skin-touch feeling agent, the viscosity of the compound (II) is 20 to 200 mPas, the viscosity of the compound (III) is 50 to 500 mPas, and the viscosity of the compound (IV) is 10 to 30 mPas.
In the skin-touch feeling agent, the viscosity of the compound (II) is 25 to 50 mPas, the viscosity of the compound (III) is 200 to 300 mPas, and the viscosity of the compound (IV) is 20 to 25 mPas.
A second aspect of the present invention relates to a process for the preparation of a skin feel benefit comprising the steps of:
a. at room temperature, putting 1-3 parts of isomeric tridecanol polyoxyethylene ether 1307, 0.1-1.5 parts of Span-80 and 0.1-1 part of Tween-80 into a container and stirring to obtain a composite emulsifier with an HLB value of 8-11;
b. stirring 65-75 parts of high molecular weight block silicone oil and 17-22 parts of composite emulsifier at 40-60 ℃ in parts by weight in a container to obtain a first mixture, wherein the high molecular weight block silicone oil has a structural general formula shown in the following formula (I):
wherein x is 110-150, y is 15-30, and z is 20-40;
c. adding 3-6 parts by weight of fumed silica into the first mixture at 40-60 ℃ and stirring to obtain a second mixture;
d. and adding 1-5 parts by weight of alkynol A04 into the second mixture at 40-60 ℃ and stirring to obtain the skin feeling hand feeling agent.
In the preparation method of the skin-feel hand feeling agent, the weight ratio of isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80 in the composite emulsifier is 2: 1: 1; the weight ratio of the high molecular weight block silicone oil to the composite emulsifier to the fumed silica to the alkynol A04 is 72: 19: 5: 4.
the skin feeling hand feeling agent provided by the method is a composite organic silicon skin feeling hand feeling agent and has soft and smooth skin feeling. The block silicone oil used in the invention has higher molecular weight, is not easy to migrate, so that the durability is high, and has a longer D chain segment (dimethyl silica chain segment), so that the smooth hand feeling is ensured. In addition, the method for preparing the block silicone oil can obtain longer continuous D-chain polymer amino silicone oil. Compared with the traditional process, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine is added as a polymerization inhibitor during silanol polymerization, so that the silanol is effectively prevented from being cohered at the high temperature of more than 100 ℃, and the high-molecular-weight blocked amino silicone oil is obtained.
In addition, when the composite organic silicon skin-feel hand feeling agent is prepared, the alkynol A04 (C) is added in the process of dispersing the active components14H26O2) The method can assist the gas-phase silicon dioxide to be directionally arranged and assist the dispersion, thereby providing excellent and fine hand feeling.
The skin-feel hand feeling agent has the characteristics of small influence on the transparency of a paint film, strong anti-fouling capability, yellowing resistance and the like, and meets the market demand better.
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
In a first aspect, the present invention provides a skin feel benefit comprising: high molecular weight block silicone oil, a composite emulsifier, fumed silica and alkynol A04, wherein the weight ratio of the high molecular weight block silicone oil to the composite emulsifier to the fumed silica to the alkynol A04 is 65-75: 17-22: 3-6: 1-5, wherein the weight ratio of the composite emulsifier to the emulsifier is 1-3: 0.1-1.5: 0.1-1 parts of isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80, wherein the HLB value is 8-11, and the high molecular weight block silicone oil has a structural general formula shown in the following formula (I):
wherein x is 110 to 150, such as 115, 120, 125, 130, 135, 140, 145 and the like, preferably 120 to 130; y is 15 to 30, such as 18, 20, 22, 25, 27, 28, 29, preferably 17 to 25; z is 20 to 40, for example, 22, 25, 27, 28, 30, 32, 35, 38, preferably 30 to 36.
The high molecular weight block silicone oil preferably has a viscosity of 5000 to 20000 mPas, for example, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000 mPas, more preferably 8000 to 10000 mPas.
In the above skin-feel hand feeling agent, the composite emulsifier (V) is a mixture of, for example, 1: 1: 1. 2: 1: 1. 3: 1: 1. 1: 0.5: 1. 1: 1: 0.5, 2: 1.5: 1, etc., preferably 2: 1: 1, isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80. The HLB value of the complex emulsifier (V) may be 8 to 11, for example 8.5, 9, 9.5, 10, 10.5 or 11, preferably 11.
1307 and Span-80 (loss of isotridecanol polyoxyethylene ether)Sorbitan fatty acid ester) and Tween-80 (polyoxyethylene sorbitan monooleate) commercially available products such as those available from the petroleum plant hei, Jiangsu. Fumed silica, for example fumed silica R106 from Woodbisattva can be used. As the alkynol A04, for example, alkynol available from Yueyang Karman aqueous adjuvant Co., Ltd
An acetylenic diol.
In the above skin-feel hand feeling agent, the high molecular weight block silicone oil is prepared by a method comprising the steps of:
a. sequentially adding 95-98 parts of N- (β -dimethylaminoethyl) -gamma-aminopropylmethyldimethoxysilane, 1-2 parts of 7% sodium hydroxide aqueous solution and 0.3-0.5 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (II):
for example, in the above steps, refluxing is carried out for 1-2 hours at 100-120 ℃, methanol is slowly distilled out, the reaction is stopped after methanol gas does not overflow, a hydrolysate is extracted by toluene, washed to be neutral by water, a water layer is separated, and toluene is removed by reduced pressure distillation, so as to obtain a linear compound (II);
b. sequentially adding 95-99 parts of octamethylcyclotetrasiloxane and 1-2 parts of 7% potassium hydroxide aqueous solution into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (III):
for example, in the above steps, the reaction is stopped after refluxing for 1 to 2 hours at 100 to 120 ℃, the hydrolysate is extracted with toluene and washed to neutrality, the water layer is separated, and the toluene is removed by reduced pressure distillation to obtain the linear compound (III);
c. sequentially adding 95-98 parts of (phenyl tert-butyl) methyldimethoxysilane, 2-3 parts of 7% sodium hydroxide aqueous solution and 0.3-0.5 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (IV):
for example, in the above steps, refluxing is carried out for 1-2 hours at 100-120 ℃, methanol is slowly distilled out, the reaction is stopped after methanol gas does not overflow, a hydrolysate is extracted by toluene, washed to be neutral by water, a water layer is separated, and toluene is removed by reduced pressure distillation, so as to obtain a linear compound (IV);
d. adding 30-38 parts of compound (II), 60-90 parts of compound (III), 15-20 parts of compound (IV) and 0.5-1 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, dehydrating and condensing at 110-120 ℃, and then adding 8-10 parts of trimethyl methoxy silane for end-capping degradation reaction to obtain the high molecular weight block silicone oil shown in formula (I).
For example, compound (II) (preferably 34-37 parts), compound (III) (preferably 70-80 parts), compound (IV) (preferably 11-13 parts) and 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine are added into a reactor, dehydrated and condensed for 30-40 minutes at the temperature of 110-120 ℃, then trimethyl methoxy silane (preferably 8 parts) is slowly added for end-capping degradation reaction, the reaction is stopped after 4-5 hours, and low-boiling substances (< -0.095mPa) are removed by pumping vacuum with an oil pump at the temperature of 110-150 ℃ to obtain the block silicone oil (I) with certain viscosity and high molecular weight.
In the above-mentioned method for producing a high-molecular-weight block silicone oil, the viscosity of the compound (II) is from 20 mPas to 200 mPas, for example, from 25, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90, 100, 120, 140, 160 or 180 mPas, preferably from 25 mPas to 50 mPas; the viscosity of the compound (III) is from 50 to 500 mPas, for example from 60, 70, 100, 200, 250, 300, 400 or 450 mPas, preferably from 200 to 300 mPas; the viscosity of the compound (IV) is from 10 mPas to 30 mPas, for example, 12, 15, 18, 20, 22, 25 or 28 mPas, preferably from 20 to 25 mPas.
In the above skin-feel hand feeling agent, the weight part of the high molecular weight block silicone oil may be, for example, 66, 67, 68, 70, 72 or 74 parts, the weight part of the composite emulsifier may be, for example, 18, 19, 20 or 21 parts, the weight part of the fumed silica may be, for example, 4 or 5 parts, the weight part of the alkynol a04 may be, for example, 2, 3 or 4 parts, and the weight ratio therebetween is preferably 72: 19: 5: 4.
the second aspect of the invention provides a preparation method of a skin-feel hand feeling agent, which comprises the following steps:
a. putting 1-3 parts (such as 1.5, 2.0 or 2.5 parts) of isomeric tridecanol polyoxyethylene ether 1307, 0.1-1.5 parts (such as 0.5 or 1 part) of Span-80 and 0.1-1 part (such as 0.5 part) of Tween-80 into a container at room temperature, and stirring to obtain a composite emulsifier with an HLB (hydrophile-lipophile balance) value of 8-11;
for example, in the above step, the dispersion may be carried out at 300 to 600r/m for 10 to 50 minutes, preferably at 500r/m for 30 minutes;
b. stirring 65-75 parts by weight of the high molecular weight block silicone oil and 17-22 parts by weight of the composite emulsifier in a container at 40-60 ℃, preferably 50 ℃ to obtain a first mixture;
for example, in the above step, the dispersion may be carried out at 300 to 600r/m for 5 to 20 minutes, preferably at 500r/m for 15 minutes;
c. adding 3-6 parts by weight of fumed silica into the first mixture at 40-60 ℃, preferably 50 ℃, and stirring to obtain a second mixture;
d. and adding 1-5 parts by weight of alkynol A04 into the second mixture at 40-60 ℃ and stirring to obtain the composite organic silicon skin-feel hand feeling agent.
Example 1
Step 1:
98g N- (β -dimethylaminoethyl) -gamma-aminopropylmethyldimethoxysilane, 2g of 7% sodium hydroxide aqueous solution and 0.5g of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine are sequentially added into a reactor, reflux is carried out for 1 hour at the temperature of 100 ℃, methanol is slowly evaporated out, the reaction is stopped after no methanol gas overflows, a hydrolysate is extracted by toluene and washed to be neutral by water, a water layer is separated, and the toluene is removed by reduced pressure distillation, so that 61.38g of a linear compound (II) with the viscosity of 30 mPas is obtained.
Step 2:
98g D4, 1g of 7% potassium hydroxide aqueous solution was sequentially added to a reactor, the reaction was stopped after refluxing at 100 ℃ for 1 hour, the hydrolyzate was extracted with toluene, washed to neutrality with water, the aqueous layer was separated, and toluene was removed by distillation under reduced pressure to obtain 81.27g of a linear compound (III), viscosity: 220 mPas.
And step 3:
sequentially adding 98g of (phenyl tert-butyl) methyldimethoxysilane, 2g of 7% sodium hydroxide aqueous solution and 0.5g of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a reactor, refluxing for 1 hour at 100 ℃, slowly evaporating methanol, stopping the reaction after no methanol gas overflows, extracting a hydrolysate by using toluene, washing the hydrolysate to be neutral, separating a water layer, and removing the toluene by reduced pressure distillation to obtain 68.51g of a linear compound (IV), wherein the viscosity of the linear compound is as follows: 25 mPas.
And 4, step 4:
adding 34g of the compound (II), 70g of the compound (III), 15g of the compound (IV) and 1g of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a reactor, dehydrating and condensing for 30 minutes at 110 ℃, then slowly adding 8g of trimethylmethoxysilane for carrying out end-capping degradation reaction, stopping the reaction after 4 hours, and removing low-boiling-point substances (< -0.095mPa) by using an oil pump for vacuumizing at 110-150 ℃ to obtain the high-molecular-weight block silicone oil (I). Viscosity: 9200 mPas.
And 5:
at room temperature, 20g of 1307, 10g of Span-80 and 10g of Tween-80 are put into a reactor according to the weight ratio and dispersed for 30 minutes at 200r/m, and the composite emulsifier (V) with the HLB value of 11 is obtained.
Step 6:
75g of the linear compound (I) and 22g of the complex emulsifier (V) were put into a reactor at 200r/m at 50 ℃ by weight ratio and dispersed for 10 minutes to obtain 97g of the mixture (VI).
And 7:
5g of fumed silica were slowly added to the mixture (VI) at 50 ℃ in terms of weight ratio and dispersed at 500r/m for 30 minutes to obtain 102g of a mixture (VII).
And 8:
3g of alkynol A04 is slowly added into the mixture (VII) according to the weight ratio at 50 ℃, and the mixture is dispersed for 30 minutes at 500r/m, so as to obtain 100g of the composite organic silicon skin-feel hand feeling agent.
Physical properties of the product are as follows:
| appearance (visual inspection) | Viscosity of the solution | Yield of step 8 |
| Viscous emulsions | 7850mPa·s | 95.24％ |
Example 1 was compared with the same type of product on the market
And (3) performing performance test on the low-oil PVC leather, and detecting skin feel, blackness and hand feeling durability.
Skin feel: the wetting agent 1% and the example 1 0.5% are added into the polyurethane resin, and after fully and uniformly stirring, the polyurethane resin is coated on the PVC leather, and after drying, the hand feeling of the PVC leather is felt by lightly stroking the surface of the PVC leather with hands.
Blackness: the wetting agent 1% and the example 1 0.5% were added to the polyurethane resin, and after sufficiently and uniformly stirring, the mixture was coated on a PU leather, and after drying, the leather blackness was observed.
And (3) hand feeling durability: adding 1% wetting agent and 0.5% example 1 into polyurethane resin, fully stirring uniformly, coating on PVC leather, drying, stroking the leather surface with hands, storing in dark for 3 months and 6 months, and stroking again to feel the hand feeling.
Example 2
Example 2 is the same as steps 1 to 3 of example 1, and steps 4 to 8 are as follows.
And 4, step 4:
adding 30g of the compound (II), 60g of the compound (III), 15g of the compound (IV) and 1g of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a reactor, dehydrating and condensing for 30 minutes at 110-150 ℃, then slowly adding 8g of trimethylmethoxysilane for end-capping degradation reaction, stopping the reaction after 4 hours, and removing low-boiling-point substances (< -0.095mPa) by using an oil pump for vacuumizing at 110 ℃ to obtain the high-molecular-weight block silicone oil (I). Viscosity: 8100 mPas.
And 5:
30g of 1307, 15g of Span-80 and 10g of Tween-80 are put into a reactor according to the weight ratio at room temperature and dispersed for 30 minutes at 200r/m to obtain the composite emulsifier (V) with the HLB value of 10.4.
Step 6:
65g of the linear compound (I) and 17g of the complex emulsifier (V) were put into a reactor at 200r/m at 50 ℃ by weight ratio and dispersed for 10 minutes to obtain 82g of the mixture (VI).
And 7:
3g of fumed silica were slowly added to mixture (VI) at 50 ℃ in terms of weight ratio and dispersed at 500r/m for 30 minutes to obtain 85g of mixture (VII).
And 8:
at 50 ℃, 1g of alkynol A04 is slowly added into the mixture (VII) according to the weight ratio, and the mixture is dispersed for 30 minutes at 500r/m, thus obtaining 83g of the composite organosilicon skin-feel hand feeling agent.
Physical properties of the product are as follows:
| appearance (visual inspection) | Viscosity of the solution | Yield of step 8 |
| Viscous emulsions | 7200mPa·s | 96.51％ |
Example 2 was compared with the same type of product on the market
And (3) performing performance test on the low-oil PVC leather, and detecting skin feel, blackness and hand feeling durability.
Example 3
Example 3 is the same as steps 1 to 3 of example 1, and steps 4 to 8 are as follows.
And 4, step 4:
adding 37g of the compound (II), 85g of the compound (III), 18g of the compound (IV) and 1g of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a reactor, dehydrating and condensing for 30 minutes at 110-150 ℃, then slowly adding 10g of trimethylmethoxysilane for end-capping degradation reaction, stopping the reaction after 4 hours, and removing low-boiling-point substances (< -0.095mPa) by using an oil pump for vacuum pumping at 120 ℃ to obtain the high-molecular-weight block silicone oil (I). Viscosity: 8100 mPas.
And 5:
10g of 1307, 10g of Span-80 and 5g of Tween-80 are put into a reactor according to the weight ratio at room temperature and dispersed for 30 minutes at 200r/m, and the composite emulsifier (V) with the HLB value of 9.5 is obtained.
Step 6:
70g of the linear compound (I) and 20g of the complex emulsifier (V) were put into a reactor at 200r/m at 50 ℃ by weight ratio and dispersed for 10 minutes to obtain 90g of the mixture (VI).
And 7:
4g of fumed silica were slowly added to mixture (VI) at 50 ℃ in terms of weight ratio and dispersed at 500r/m for 30 minutes to obtain 94g of mixture (VII).
And 8:
4g of alkynol A04 was slowly added to the mixture (VII) at 50 ℃ in terms of weight ratio, and dispersed at 500r/m for 30 minutes to obtain 92g of a composite silicone skin-feel hand feeling agent.
Physical properties of the product are as follows:
| appearance (visual inspection) | Viscosity of the solution | Yield of step 8 |
| Viscous emulsions | 7550mPa·s | 93.88％ |
Example 3 is compared with the same type of product on the market
And (3) performing performance test on the low-oil PVC leather, and detecting skin feel, blackness and hand feeling durability.
Comparative example 1
The skin-feel hand feeling agent in comparative example 1 was the same as example 1 except that the high molecular weight block silicone oil of formula (I) was replaced with a silicone oil of the following formula:
comparative example 1 and the same type of product on the market
And (3) performing performance test on the low-oil PVC leather, and detecting skin feel, blackness and hand feeling durability.
Comparative example 2
The skin feel hand feel in comparative example 2 was the same as example 1 except that the alkynol a04 was not used. Comparative example 2 and the same type of product on the market
And (3) performing performance test on the low-oil PVC leather, and detecting skin feel, blackness and hand feeling durability.
Comparative example 3
The skin-feel hand feeling agent in comparative example 3 was the same as example 1 except that the complex emulsifier was replaced with Tween-80. Comparative example 3 is compared with the same type of product on the market
And (3) performing performance test on the low-oil PVC leather, and detecting skin feel, blackness and hand feeling durability.
Comparative example 4
Skin feel agent in comparative example 4 except thatThe procedure of example 1 was repeated except that ordinary silica was used. Comparative example 4 was compared with the same type of product on the market
And (3) performing performance test on the low-oil PVC leather, and detecting skin feel, blackness and hand feeling durability.
In addition, the inventor tests the performances of the skin-feel hand feeling agent of the invention, such as paint film transparency, stain resistance, yellowing resistance, and the like, and the performances are far superior to those of the existing products.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A skin-feel hand preparation comprising: high molecular weight block silicone oil, a composite emulsifier, fumed silica and alkynol A04, wherein the weight ratio of the high molecular weight block silicone oil to the composite emulsifier to the fumed silica to the alkynol A04 is 65-75: 17-22: 3-6: 1-5, wherein the weight ratio of the composite emulsifier to the emulsifier is 1-3: 0.1-1.5: 0.1-1 parts of isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80, wherein the HLB value is 8-11, and the high molecular weight block silicone oil has a structural general formula shown in the following formula (I):
wherein x is 110-150, y is 15-30, and z is 20-40.
2. The skin-feel hand feeling agent according to claim 1, wherein the viscosity of the high-molecular-weight block silicone oil is from 5000 mPa-s to 20000 mPa-s.
3. The skin-feel hand feeling agent according to claim 2, wherein the viscosity of the high molecular weight block silicone oil is 8000 to 10000 mPa-s.
4. The skin feel hand feel agent of claim 1 wherein said complex emulsifier is a blend of 2: 1: 1, isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80.
5. Skin feel hand feel agent according to claim 1, characterized in that the weight ratio between said high molecular weight block silicone oil, said complex emulsifier, said fumed silica and said alkynol a04 is 72: 19: 5: 4.
6. skin feel hand according to claim 1, characterized in that said high molecular weight block silicone oil is prepared by a process comprising the steps of:
a. sequentially adding 90-98 parts of N- (β -dimethylaminoethyl) -gamma-aminopropylmethyldimethoxysilane, 2-5 parts of 7 mass percent sodium hydroxide aqueous solution and 0.3-0.5 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (II):
b. sequentially adding 95-99 parts of octamethylcyclotetrasiloxane and 1-3 parts of 7% (by mass) potassium hydroxide aqueous solution into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (III):
c. sequentially adding 90-98 parts of (phenyl tert-butyl) methyldimethoxysilane, 2-5 parts of 7 mass% of sodium hydroxide aqueous solution and 0.3-0.5 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, and carrying out reflux reaction at 100-120 ℃ to obtain the following compound (IV):
d. adding 30-38 parts of compound (II), 60-90 parts of compound (III), 15-20 parts of compound (IV) and 0.5-1 part of 1, 1-diphenyl-2- (2,4, 6-trinitrobenzene) hydrazine into a container, dehydrating and condensing at 110-120 ℃, and then adding 8-10 parts of trimethyl methoxy silane for end-capping degradation reaction to obtain the high molecular weight block silicone oil shown in formula (I).
7. The skin-feel hand feeling agent according to claim 6, wherein the viscosity of compound (II) is from 20 mPas to 200 mPas, the viscosity of compound (III) is from 50 mPas to 500 mPas, and the viscosity of compound (IV) is from 10 mPas to 30 mPas.
8. The skin-feel hand feeling agent according to claim 7, wherein the viscosity of compound (II) is from 25 mPas to 50 mPas, the viscosity of compound (III) is from 200 mPas to 300 mPas, and the viscosity of compound (IV) is from 20 mPas to 25 mPas.
9. A preparation method of a skin-feel hand feeling agent is characterized by comprising the following steps:
a. at room temperature, putting 1-3 parts of isomeric tridecanol polyoxyethylene ether 1307, 0.1-1.5 parts of Span-80 and 0.1-1 part of Tween-80 into a container and stirring to obtain a composite emulsifier with an HLB value of 8-11;
b. stirring 65-75 parts of high molecular weight block silicone oil and 17-22 parts of the composite emulsifier at 40-60 ℃ in parts by weight in a container to obtain a first mixture, wherein the high molecular weight block silicone oil has a structural general formula shown in the following formula (I):
wherein x is 110-150, y is 15-30, and z is 20-40;
c. adding 3-6 parts by weight of fumed silica into the first mixture at 40-60 ℃ and stirring to obtain a second mixture;
d. and adding 1-5 parts by weight of alkynol A04 into the second mixture at 40-60 ℃ and stirring to obtain the skin feeling hand feeling agent.
10. The preparation method of the skin-feel hand feeling agent as claimed in claim 9, wherein the weight ratio of isomeric tridecanol polyoxyethylene ether 1307, Span-80 and Tween-80 in the composite emulsifier is 2: 1: 1; the weight ratio of the high molecular weight block silicone oil to the composite emulsifier to the fumed silica to the alkynol A04 is 72: 19: 5: 4.
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