CN117089210B - Silicon rubber for medical protection and preparation method thereof - Google Patents
Silicon rubber for medical protection and preparation method thereof Download PDFInfo
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- CN117089210B CN117089210B CN202311344649.0A CN202311344649A CN117089210B CN 117089210 B CN117089210 B CN 117089210B CN 202311344649 A CN202311344649 A CN 202311344649A CN 117089210 B CN117089210 B CN 117089210B
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000004945 silicone rubber Substances 0.000 claims abstract description 45
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 230000004048 modification Effects 0.000 claims abstract description 19
- 238000012986 modification Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 116
- 229920002472 Starch Polymers 0.000 claims description 75
- 239000008107 starch Substances 0.000 claims description 72
- 235000019698 starch Nutrition 0.000 claims description 72
- -1 methyl vinyl Chemical group 0.000 claims description 44
- 229920002545 silicone oil Polymers 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 30
- 229920002554 vinyl polymer Polymers 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 27
- 229920001296 polysiloxane Polymers 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 18
- 235000013339 cereals Nutrition 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021485 fumed silica Inorganic materials 0.000 claims description 12
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical group C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 10
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920002261 Corn starch Polymers 0.000 claims description 8
- 239000008120 corn starch Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 abstract description 9
- 238000002834 transmittance Methods 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 229920000058 polyacrylate Polymers 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 5
- 229920000881 Modified starch Polymers 0.000 description 4
- 239000004368 Modified starch Substances 0.000 description 4
- 235000019426 modified starch Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of liquid silicone rubber, in particular to silicone rubber for medical protection and a preparation method thereof. The invention forms a combination of starch-polyacrylate-nano silicon dioxide through acrylate grafting reaction, and the combination is dispersed in the base adhesive. When the dispersion system receives stress such as stretching and vibration, the nano silicon dioxide generates stress concentration points, the nano silicon dioxide is broken with starch-polyacrylate serving as an organic phase, the starch-polyacrylate generates silver grains to absorb energy, and then under the condition of further receiving stress, the interface between the starch-polyacrylate and the base adhesive is separated, so that the base adhesive generates cracks, and finally, the integral material generates irreversible plastic damage. Compared with the modification by independently adding the nano silicon dioxide, the strength of the starch-polyacrylate-nano silicon dioxide connector for improving the rigidity is limited, but the toughness of the silicon rubber is obviously improved, and the light transmittance is also better improved.
Description
Technical Field
The invention relates to the technical field of liquid silicone rubber, in particular to silicone rubber for medical protection and a preparation method thereof.
Background
As an emerging organosilicon downstream product, the addition type Liquid Silicone Rubber (LSR) is a novel organosilicon material which is nontoxic and odorless, has excellent weather resistance and chemical inertness, has high production efficiency and good product quality, and is popular in the market. Compared with free radical crosslinking liquid silicone rubber or polycondensation liquid silicone rubber, the addition type silicone rubber has the characteristics of low-temperature vulcanization, simple process, easy automatic production and the like, and is more suitable for industrial production. The addition type liquid silicone rubber is safe and nontoxic, has good chemical stability and biocompatibility, and does not generate byproducts in the vulcanization process, so that the addition type liquid silicone rubber is widely used in medical supplies.
The addition-type liquid silicone rubber generally consists of a base rubber, a crosslinking agent, a catalyst, an inhibitor and a filler, wherein the filler plays roles of reinforcing strength and adjusting viscosity. Common fillers include titanium dioxide, white carbon, graphene, carbon black, calcium carbonate, and the like. As the filler increases, the strength of the silicone rubber increases, but as the solids content increases, the transparency tends to decrease. For medical supplies such as medical catheters, transparency is an important property, so how to coordinate the relationship of reinforcement and stability is an important issue for research.
Disclosure of Invention
In order to overcome the defects and the shortcomings in the prior art, the invention aims to provide the high-strength high-stability silicone rubber for medical protection and a preparation method thereof.
The aim of the invention is achieved by the following technical scheme:
a preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 120-160 parts by weight of starch, 8-12 parts by weight of methyl acrylate, 8-10 parts by weight of butyl acrylate, 8-10 parts by weight of ethyl acrylate, 5-7 parts by weight of acrylic acid and 0.1-0.3 part by weight of initiator into 100 parts by weight of water, stirring for 8-12min, heating to 70-80 ℃, continuing to keep the temperature and stir for 2-3h, adding 6-8 parts by weight of trimethylolpropane triacrylate, continuing to keep the temperature and stir for 0.5-1.5h, then adding 20-30 parts by weight of nano silicon dioxide, 8-12 parts by weight of butyl acrylate, 8-12 parts by weight of ethyl acrylate, 4-6 parts by weight of acrylic acid, 1-3 parts by weight of N-N' -methylenebisacrylamide and 0.1-0.3 part by weight of initiator, continuing to keep the temperature and stir for 2-3h, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 8-12 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 8-12min, adding 8-12 parts by weight of the starch modification body obtained in the step (1), stirring for 8-12min, adding 6-10 parts by weight of gas-phase white carbon black, stirring for 8-12min, adding 0.1-0.3 part by weight of vinyl silicone oil and 0.02-0.1 part by weight of catalyst, and stirring for 8-12min to obtain the component A of the silicone rubber for medical protection; adding 10-20 parts by weight of fumed silica, 1-3 parts by weight of hydrogen-containing silicone oil and 0.02-0.1 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 8-12min to obtain the component B of the silicone rubber for medical protection.
Preferably, in the step (1), the starch is at least one of tapioca starch, corn starch and wheat starch, the average particle size of the starch is 25-35 μm, and the average particle size of the nano silicon dioxide is 20-40nm.
Preferably, in the step (1), the stirring is ball milling stirring, the ball-material ratio is 8-10:1, the grinding medium is silicon carbide balls, and the diameter is 8-12mm.
Preferably, in the step (1), the initiator is ammonium persulfate or potassium persulfate.
Preferably, in step (2), the stirring speed is 1000-2000rpm.
Preferably, in step (2), the vinyl content of the methylvinylpolysiloxane is from 0.1 to 0.2mol% and the viscosity at 25℃is from 5000 to 7000 mpa.s.
Preferably, in the step (2), the hydrogen content of the hydrogen-containing silicone oil is 2.5-3.5%, the viscosity at 25 ℃ is 30-40mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 18000-22000mpa.s.
Preferably, in the step (2), the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
The invention has the beneficial effects that:
compared with the conventional reinforcing filler, the starch has the advantages that the starch is similar to the conventional silica filler, the content of surface hydroxyl groups is rich, the starch is difficult to infiltrate and disperse in an organic medium, but the starch has the reinforcing property which is inferior to that of inorganic rigid particles, so that the starch is not generally adopted for reinforcing in the field of silicone rubber. However, the starch has the advantages that the starch is an environment-friendly biological material, has predictable safety when applied to the field of medical supplies, has certain light transmittance, and is more beneficial to the improvement of the light transmittance compared with an opaque inorganic rigid body.
The invention does not directly modify the functional groups of the starch to solve the problem of compatibility, because even after the problem of compatibility is solved, the modified starch has more dispersed states of monodispersion or local agglomeration in the base rubber, and the strength of the starch is inferior to that of a conventional reinforcing filler, and the toughness is inferior to that of the base rubber, so that the modified starch cannot play a role in improving the mechanical property of the silicone rubber.
According to the invention, through acrylate grafting reaction, on one hand, the multifunctional trimethylolpropane triacrylate is introduced on starch grafting modification, so that starch and acrylate monomers can form a pre-crosslinked structure, the hardness of the starch is improved, more active functional groups are formed, and on the other hand, the N-N' -methylene bisacrylamide which can be strongly crosslinked with the starch is introduced on the other hand, so that a starch-polyacrylate-nano silica connector is formed and dispersed in the base adhesive. When the dispersion system is subjected to stress such as stretching and vibration, the nano silicon dioxide generates stress concentration points, the nano silicon dioxide is broken with starch-polyacrylate serving as an organic phase, the starch-polyacrylate generates silver grains to absorb energy, and then under the condition of further stress, the interface between the starch-polyacrylate and the base adhesive is separated, so that the base adhesive generates cracks, and finally, the integral material generates irreversible plastic damage. Compared with the modification by independently adding the nano silicon dioxide, the strength of the starch-polyacrylate-nano silicon dioxide connector for improving the rigidity is limited, but the toughness of the silicon rubber is obviously improved, and the light transmittance is also better improved.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1
A preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 140 parts by weight of starch, 10 parts by weight of methyl acrylate, 9 parts by weight of butyl acrylate, 9 parts by weight of ethyl acrylate, 6 parts by weight of acrylic acid and 0.2 part by weight of initiator into 100 parts by weight of water, stirring for 10min, heating to 75 ℃, continuing to stir for 2.5h at a constant temperature, adding 7 parts by weight of trimethylolpropane triacrylate, continuing to stir for 1h at a constant temperature, then adding 25 parts by weight of nano silicon dioxide, 10 parts by weight of butyl acrylate, 10 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, 2 parts by weight of N-N' -methylenebisacrylamide and 0.2 part by weight of initiator, continuing to stir for 2.5h at a constant temperature, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 10 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 10min, adding 10 parts by weight of the starch modification body obtained in the step (1), stirring for 10min, adding 8 parts by weight of gas-phase white carbon black, stirring for 10min, adding 0.2 part by weight of vinyl silicone oil and 0.05 part by weight of catalyst, and stirring for 10min to obtain the component A of the medical protection silicone rubber; and adding 15 parts by weight of fumed silica, 2 parts by weight of hydrogen-containing silicone oil and 0.05 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 10min to obtain the component B of the silicone rubber for medical protection.
In the step (1), the starch is corn starch, the average grain size of the starch is 30 mu m, and the average grain size of the nano silicon dioxide is 30nm.
In the step (1), the stirring is ball milling stirring, the ball-material ratio is 9:1, the grinding medium is silicon carbide balls, and the diameter is 10mm.
In the step (1), the initiator is ammonium persulfate.
In step (2), the stirring speed was 1500rpm.
In step (2), the vinyl content of the methylvinylpolysiloxane was 0.15mol% and the viscosity at 25℃was 6000 mpa.s.
In the step (2), the hydrogen content of the hydrogen-containing silicone oil is 3%, the viscosity at 25 ℃ is 35mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 20000mpa.s.
And (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
Example 2
A preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 120 parts by weight of starch, 8 parts by weight of methyl acrylate, 8-parts by weight of butyl acrylate, 8-parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid and 0.1 part by weight of initiator into 100 parts by weight of water, stirring for 8min, heating to 80 ℃, continuing to stir for 2h at a constant temperature, adding 6 parts by weight of trimethylolpropane triacrylate, continuing to stir for 0.5h at a constant temperature, then adding 20 parts by weight of nano silicon dioxide, 8 parts by weight of butyl acrylate, 8 parts by weight of ethyl acrylate, 4 parts by weight of acrylic acid, 1-3 parts by weight of N-N' -methylenebisacrylamide and 0.1 part by weight of initiator, continuing to stir for 2h at a constant temperature, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 8 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 8min, adding 8 parts by weight of the starch modification body obtained in the step (1), stirring for 8min, adding 6 parts by weight of gas-phase white carbon black, stirring for 8min, adding 0.1 part by weight of vinyl silicone oil and 0.02 part by weight of catalyst, and stirring for 8min to obtain the component A of the medical protection silicone rubber; and adding 10 parts by weight of fumed silica, 1 part by weight of hydrogen-containing silicone oil and 0.02 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 8min to obtain the component B of the silicone rubber for medical protection.
In the step (1), the starch is wheat starch, the average grain size of the starch is 25 mu m, and the average grain size of the nano silicon dioxide is 20nm.
In the step (1), the stirring is ball milling stirring, the ball-material ratio is 8:1, the grinding medium is silicon carbide balls, and the diameter is 8mm.
In the step (1), the initiator is potassium persulfate.
In step (2), the stirring speed was 1000rpm.
In step (2), the vinyl content of the methylvinylpolysiloxane was 0.1mol% and the viscosity at 25℃was 5000 mpa.s.
In the step (2), the hydrogen content of the hydrogen-containing silicone oil is 2.5%, the viscosity at 25 ℃ is 30mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 18000mpa.s.
And (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
Example 3
A preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 160 parts by weight of starch, 12 parts by weight of methyl acrylate, 10 parts by weight of butyl acrylate, 10 parts by weight of ethyl acrylate, 7 parts by weight of acrylic acid and 0.3 part by weight of initiator into 100 parts by weight of water, stirring for 12min, heating to 80 ℃, continuing to keep the temperature and stir for 3h, adding 8 parts by weight of trimethylolpropane triacrylate, continuing to keep the temperature and stir for 1.5h, then adding 30 parts by weight of nano silicon dioxide, 12 parts by weight of butyl acrylate, 12 parts by weight of ethyl acrylate, 6 parts by weight of acrylic acid, 3 parts by weight of N-N' -methylenebisacrylamide and 0.3 part by weight of initiator, continuing to keep the temperature and stir for 3h, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 12 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 12min, adding 12 parts by weight of the starch modification body obtained in the step (1), stirring for 12min, adding 10 parts by weight of gas-phase white carbon black, stirring for 12min, adding 0.3 part by weight of vinyl silicone oil and 0.1 part by weight of catalyst, and stirring for 12min to obtain the component A of the medical protection silicone rubber; and adding 20 parts by weight of fumed silica, 3 parts by weight of hydrogen-containing silicone oil and 0.1 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 12min to obtain the component B of the silicone rubber for medical protection.
In the step (1), the starch is tapioca starch, the average grain size of the starch is 35 mu m, and the average grain size of the nano silicon dioxide is 40nm.
In the step (1), the stirring is ball milling stirring, the ball-material ratio is 10:1, the grinding medium is silicon carbide balls, and the diameter is 12mm.
In the step (1), the initiator is potassium persulfate.
In step (2), the stirring speed was 2000rpm.
In step (2), the vinyl content of the methyl vinyl polysiloxane was 0.2mol%, and the viscosity at 25℃was 7000 mpa.s.
In the step (2), the hydrogen content of the hydrogen-containing silicone oil is 3.5%, the viscosity at 25 ℃ is 40mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 22000mpa.s.
And (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
Example 4
A preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 130 parts by weight of starch, 10 parts by weight of methyl acrylate, 9 parts by weight of butyl acrylate, 8 parts by weight of ethyl acrylate, 7 parts by weight of acrylic acid and 0.1 part by weight of initiator into 100 parts by weight of water, stirring for 10min, heating to 80 ℃, continuing to keep the temperature and stir for 3h, adding 8 parts by weight of trimethylolpropane triacrylate, continuing to keep the temperature and stir for 1h, then adding 23 parts by weight of nano silicon dioxide, 9 parts by weight of butyl acrylate, 11 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, 1 part by weight of N-N' -methylenebisacrylamide and 0.2 part by weight of initiator, continuing to keep the temperature and stir for 2-3h, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 12 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 8min, adding 11 parts by weight of the starch modification body obtained in the step (1), stirring for 9min, adding 7 parts by weight of gas-phase white carbon black, stirring for 11min, adding 0.2 part by weight of vinyl silicone oil and 0.04 part by weight of catalyst, and stirring for 10min to obtain the component A of the medical protection silicone rubber; and adding 18 parts by weight of fumed silica, 1 part by weight of hydrogen-containing silicone oil and 0.03 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 10min to obtain the component B of the silicone rubber for medical protection.
In the step (1), the starch is corn starch, the average grain size of the starch is 30 mu m, and the average grain size of the nano silicon dioxide is 25nm.
In the step (1), the stirring is ball milling stirring, the ball-material ratio is 9:1, the grinding medium is silicon carbide balls, and the diameter is 10mm.
In the step (1), the initiator is ammonium persulfate.
In step (2), the stirring speed was 1500rpm.
In step (2), the vinyl content of the methylvinylpolysiloxane was 0.15mol% and the viscosity at 25℃was 6000 mpa.s.
In the step (2), the hydrogen content of the hydrogen-containing silicone oil is 3%, the viscosity at 25 ℃ is 35mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 20000mpa.s.
And (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
Example 5
A preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 150 parts by weight of starch, 11 parts by weight of methyl acrylate, 9 parts by weight of butyl acrylate, 8 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid and 0.3 part by weight of initiator into 100 parts by weight of water, stirring for 12min, heating to 70 ℃, continuing to stir for 2h under heat preservation, adding 8 parts by weight of trimethylolpropane triacrylate, continuing to stir for 1h under heat preservation, then adding 27 parts by weight of nano silicon dioxide, 11 parts by weight of butyl acrylate, 11 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, 2 parts by weight of N-N' -methylenebisacrylamide and 0.3 part by weight of initiator, continuing to stir for 2.5h under heat preservation, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 11 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 11min, adding 9 parts by weight of the starch modification body obtained in the step (1), stirring for 10min, adding 7 parts by weight of gas-phase white carbon black, stirring for 10min, adding 0.12 part by weight of vinyl silicone oil and 0.08 part by weight of catalyst, and stirring for 10min to obtain the component A of the medical protection silicone rubber; and adding 13 parts by weight of fumed silica, 2 parts by weight of hydrogen-containing silicone oil and 0.07 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 10min to obtain the component B of the silicone rubber for medical protection.
In the step (1), the starch is corn starch, the average grain size of the starch is 30 mu m, and the average grain size of the nano silicon dioxide is 20nm.
In the step (1), the stirring is ball milling stirring, the ball-material ratio is 9:1, the grinding medium is silicon carbide balls, and the diameter is 10mm.
In the step (1), the initiator is ammonium persulfate.
In step (2), the stirring speed was 1500rpm.
In step (2), the vinyl content of the methylvinylpolysiloxane was 0.15mol% and the viscosity at 25℃was 6000 mpa.s.
In the step (2), the hydrogen content of the hydrogen-containing silicone oil is 3%, the viscosity at 25 ℃ is 35mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 20000mpa.s.
And (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
Comparative example 1
A preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 140 parts by weight of starch, 10 parts by weight of methyl acrylate, 9 parts by weight of butyl acrylate, 9 parts by weight of ethyl acrylate, 6 parts by weight of acrylic acid and 0.2 part by weight of initiator into 100 parts by weight of water, stirring for 10min, heating to 75 ℃, continuing to stir for 2.5h at a constant temperature, adding 7 parts by weight of trimethylolpropane triacrylate, continuing to stir for 1h at a constant temperature, then continuing to stir for 2.5h at a constant temperature of 10 parts by weight of butyl acrylate, 10 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, 2 parts by weight of N-N' -methylenebisacrylamide and 0.2 part by weight of initiator, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 10 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 10min, adding 10 parts by weight of the starch modification body obtained in the step (1), stirring for 10min, adding 8 parts by weight of gas-phase white carbon black, stirring for 10min, adding 0.2 part by weight of vinyl silicone oil and 0.05 part by weight of catalyst, and stirring for 10min to obtain the component A of the medical protection silicone rubber; and adding 15 parts by weight of fumed silica, 2 parts by weight of hydrogen-containing silicone oil and 0.05 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 10min to obtain the component B of the silicone rubber for medical protection.
In the step (1), the starch is corn starch, and the average grain size of the starch is 30 mu m.
In the step (1), the stirring is ball milling stirring, the ball-material ratio is 9:1, the grinding medium is silicon carbide balls, and the diameter is 10mm.
In the step (1), the initiator is ammonium persulfate.
In step (2), the stirring speed was 1500rpm.
In step (2), the vinyl content of the methylvinylpolysiloxane was 0.15mol% and the viscosity at 25℃was 6000 mpa.s.
In the step (2), the hydrogen content of the hydrogen-containing silicone oil is 3%, the viscosity at 25 ℃ is 35mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 20000mpa.s.
And (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
Comparative example 2
A preparation method of silicone rubber for medical protection comprises the following steps:
(1) Adding 10 parts by weight of methyl acrylate, 9 parts by weight of butyl acrylate, 9 parts by weight of ethyl acrylate, 6 parts by weight of acrylic acid and 0.2 part by weight of initiator into 100 parts by weight of water, stirring for 10min, heating to 75 ℃, continuing to stir for 2.5h at a constant temperature, adding 7 parts by weight of trimethylolpropane triacrylate, continuing to stir for 1h at a constant temperature, then adding 25 parts by weight of nano silicon dioxide, 10 parts by weight of butyl acrylate, 10 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, 2 parts by weight of N-N' -methylenebisacrylamide and 0.2 part by weight of initiator, continuing to stir for 2.5h at a constant temperature, filtering, washing and drying to obtain a modified body;
(2) Adding 10 parts by weight of the modified body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane under the protection of nitrogen, stirring for 10min, adding 10 parts by weight of the modified body obtained in the step (1), stirring for 10min, adding 8 parts by weight of fumed silica, stirring for 10min, adding 0.2 part by weight of vinyl silicone oil and 0.05 part by weight of catalyst, and stirring for 10min to obtain the component A of the medical protection silicone rubber; and adding 15 parts by weight of fumed silica, 2 parts by weight of hydrogen-containing silicone oil and 0.05 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 10min to obtain the component B of the silicone rubber for medical protection.
In the step (1), the starch is corn starch, and the average grain size of the starch is 30 mu m.
In the step (1), the stirring is ball milling stirring, the ball-material ratio is 9:1, the grinding medium is silicon carbide balls, the diameter is 10mm, and the average particle size of the nano silicon dioxide is 30nm.
In the step (1), the initiator is ammonium persulfate.
In step (2), the stirring speed was 1500rpm.
In step (2), the vinyl content of the methylvinylpolysiloxane was 0.15mol% and the viscosity at 25℃was 6000 mpa.s.
In the step (2), the hydrogen content of the hydrogen-containing silicone oil is 3%, the viscosity at 25 ℃ is 35mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 20000mpa.s.
And (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
Comparative example 3
A preparation method of silicone rubber for medical protection comprises the following steps:
under the protection of nitrogen, adding 5 parts by weight of starch and 5 parts by weight of nano silicon dioxide into 50 parts by weight of methyl vinyl polysiloxane, stirring for 10min, adding 5 parts by weight of starch and 5 parts by weight of nano silicon dioxide, stirring for 10min, adding 8 parts by weight of fumed silica, stirring for 10min, adding 0.2 part by weight of vinyl silicone oil and 0.05 part by weight of catalyst, and stirring for 10min to obtain the component A of the medical protection silicone rubber; and adding 15 parts by weight of fumed silica, 2 parts by weight of hydrogen-containing silicone oil and 0.05 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 10min to obtain the component B of the silicone rubber for medical protection.
The starch is corn starch, the average grain size of the starch is 30 mu m, and the average grain size of the nano silicon dioxide is 30nm.
The stirring is ball milling stirring, the ball-material ratio is 9:1, the grinding medium is silicon carbide balls, and the diameter is 10mm.
The stirring speed was 1500rpm.
The vinyl content of the methylvinylpolysiloxane was 0.15mol% and the viscosity at 25℃was 6000 mpa.s.
The hydrogen content of the hydrogen-containing silicone oil is 3%, the viscosity at 25 ℃ is 35mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 20000mpa.s.
The catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
The two-component silicone rubbers obtained in example 1 and comparative examples 1 to 3 were mixed in a ratio of A, B to prepare a standard test piece at 120℃for 5min, the tensile strength, elongation and tear strength were tested according to the GB/T528-2009 standard, the two-component silicone rubbers were stored alone for 6 months, and then mixed in a ratio of A, B to prepare a standard test piece at 120℃for 5min, the tensile strength, elongation and tear strength were tested according to the GB/T528-2009 standard, and the light transmittance was tested according to the GB/T2410-2008, the test results were as follows:
as is clear from the above comparative test, the modified starch of comparative example 1 was not added with nanosilica, and therefore had a significant decrease in tensile strength and tear strength, and a certain increase in elongation and light transmittance, but relatively, the loss of tensile strength and tear strength was larger, and the modified starch of comparative example 2 was not added with starch, and therefore had significant advantages in both tensile strength and tear strength, but relatively, elongation and light transmittance were also significantly lost. Comparative example 3 corresponds to a physical mixture of nanosilica and starch as the modifier, each property being at a moderate level, but tensile strength and tear strength are not significantly advantageous over the present invention, and tensile and light transmittance are significantly disadvantageous.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (9)
1. A preparation method of silicone rubber for medical protection is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding 120-160 parts by weight of starch, 8-12 parts by weight of methyl acrylate, 8-10 parts by weight of butyl acrylate, 8-10 parts by weight of ethyl acrylate, 5-7 parts by weight of acrylic acid and 0.1-0.3 part by weight of initiator into 100 parts by weight of water, stirring for 8-12min, heating to 70-80 ℃, continuing to keep the temperature and stir for 2-3h, adding 6-8 parts by weight of trimethylolpropane triacrylate, continuing to keep the temperature and stir for 0.5-1.5h, then adding 20-30 parts by weight of nano silicon dioxide, 8-12 parts by weight of butyl acrylate, 8-12 parts by weight of ethyl acrylate, 4-6 parts by weight of acrylic acid, 1-3 parts by weight of N, N' -methylenebisacrylamide and 0.1-0.3 part by weight of initiator, continuing to keep the temperature and stir for 2-3h, filtering, washing and drying to obtain a starch modified body;
(2) Under the protection of nitrogen, adding 8-12 parts by weight of the starch modification body obtained in the step (1) into 50 parts by weight of methyl vinyl polysiloxane, stirring for 8-12min, adding 8-12 parts by weight of the starch modification body obtained in the step (1), stirring for 8-12min, adding 6-10 parts by weight of gas-phase white carbon black, stirring for 8-12min, adding 0.1-0.3 part by weight of vinyl silicone oil and 0.02-0.1 part by weight of catalyst, and stirring for 8-12min to obtain the component A of the silicone rubber for medical protection; adding 10-20 parts by weight of fumed silica, 1-3 parts by weight of hydrogen-containing silicone oil and 0.02-0.1 part by weight of inhibitor into 50 parts by weight of methyl vinyl polysiloxane, and stirring for 8-12min to obtain the component B of the silicone rubber for medical protection.
2. The method for preparing the silicone rubber for medical protection according to claim 1, wherein the method comprises the following steps: in the step (1), the starch is at least one of tapioca starch, corn starch and wheat starch, the average grain size of the starch is 25-35 mu m, and the average grain size of the nano silicon dioxide is 20-40nm.
3. The method for preparing the silicone rubber for medical protection according to claim 1, wherein the method comprises the following steps: in the step (1), the stirring is ball milling stirring, the ball-material ratio is 8-10:1, the grinding medium is silicon carbide balls, and the diameter is 8-12mm.
4. The method for preparing the silicone rubber for medical protection according to claim 1, wherein the method comprises the following steps: in the step (1), the initiator is ammonium persulfate or potassium persulfate.
5. The method for preparing the silicone rubber for medical protection according to claim 1, wherein the method comprises the following steps: in step (2), the stirring speed is 1000-2000rpm.
6. The method for preparing the silicone rubber for medical protection according to claim 1, wherein the method comprises the following steps: in step (2), the vinyl content of the methyl vinyl polysiloxane is 0.1 to 0.2mol% and the viscosity at 25 ℃ is 5000 to 7000 mpa.s.
7. The method for preparing the silicone rubber for medical protection according to claim 1, wherein the method comprises the following steps: in the step (2), the hydrogen content of the hydrogen-containing silicone oil is 2.5-3.5%, the viscosity at 25 ℃ is 30-40mpa.s, and the viscosity at 25 ℃ of the vinyl silicone oil is 18000-22000mpa.s.
8. The method for preparing the silicone rubber for medical protection according to claim 1, wherein the method comprises the following steps: and (2) the catalyst is a platinum catalyst, and the inhibitor is ethynyl cyclohexanol.
9. A silicone rubber for medical protection, which is characterized in that: a process according to any one of claims 1 to 8.
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