CN114289069A - Single-component platinum catalyst and preparation method and application thereof - Google Patents
Single-component platinum catalyst and preparation method and application thereof Download PDFInfo
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- CN114289069A CN114289069A CN202111669403.1A CN202111669403A CN114289069A CN 114289069 A CN114289069 A CN 114289069A CN 202111669403 A CN202111669403 A CN 202111669403A CN 114289069 A CN114289069 A CN 114289069A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 27
- 239000004945 silicone rubber Substances 0.000 claims abstract description 25
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 14
- 125000005012 alkyl thioether group Chemical group 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkyl sulfide Chemical compound 0.000 claims description 6
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OPMRTBDRQRSNDN-UHFFFAOYSA-N Diethyl trisulfide Chemical compound CCSSSCC OPMRTBDRQRSNDN-UHFFFAOYSA-N 0.000 claims description 3
- SNGRPWPVGSSZGV-UHFFFAOYSA-N Ethyl propyl disulfide Chemical compound CCCSSCC SNGRPWPVGSSZGV-UHFFFAOYSA-N 0.000 claims description 3
- XFSWEOBOOZNZKZ-UHFFFAOYSA-N (ethyltetrasulfanyl)ethane Chemical compound CCSSSSCC XFSWEOBOOZNZKZ-UHFFFAOYSA-N 0.000 claims description 2
- QEYJAENSRLNDFW-UHFFFAOYSA-N Butyl ethyl disulfide Chemical compound CCCCSSCC QEYJAENSRLNDFW-UHFFFAOYSA-N 0.000 claims description 2
- XLTBPTGNNLIKRW-UHFFFAOYSA-N methyldisulfanylethane Chemical compound CCSSC XLTBPTGNNLIKRW-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 13
- 238000004073 vulcanization Methods 0.000 abstract description 8
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 1
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 description 1
- NQNFKQOIDNMNBB-UHFFFAOYSA-L dichloroplatinum;triphenylphosphane Chemical compound Cl[Pt]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NQNFKQOIDNMNBB-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Abstract
The invention provides a single-component platinum catalyst and a preparation method and application thereof, wherein the catalyst comprises the following raw materials in parts by weight: 5-8 parts of chloroplatinic acid, 1-5 parts of alkyl thioether, 30-50 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, 10-20 parts of sodium bicarbonate, 90-150 parts of absolute ethyl alcohol and 0.5-1 part of adsorbent. The invention adopts alkyl thioether and 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane to carry out complexation with platinum, and the obtained platinum catalyst is applied to addition type silicone rubber, so that the addition type silicone rubber has low initial vulcanization temperature and long storage time. The experimental results show that: the initial vulcanization temperature of the addition type silicone rubber is 98-108 ℃, and the room temperature storage time is more than 230 h; the storage time at 50 ℃ is 58-71 days.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a single-component platinum catalyst, and a preparation method and application thereof.
Background
The addition type silicon rubber is generally divided into two components A/B, when in use, the components A/B are uniformly mixed according to a certain proportion, and are quickly cured under a heating condition or slowly cured at room temperature, wherein the curing mechanism is that silicon vinyl in vinyl polysiloxane and silicon hydrogen bond in hydrogen-containing polysiloxane generate addition reaction under the action of a catalyst. Currently, the catalyst widely used is a platinum-on-cassett catalyst in which platinum is complexed with vinyl double head (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane). The Kanst platinum catalyst also has certain catalytic activity at low temperature, so that the addition type silicone rubber A/B component can generate crosslinking reaction at room temperature after being mixed, the viscosity is increased to a certain degree and cannot be used for construction, generally, an inhibitor for inhibiting the activity of the Kanst platinum catalyst is added to obtain certain service life, but the service life is shorter. Therefore, the development and application of the single-component platinum catalyst to addition type silicone rubber are urgent, the single-component platinum catalyst has longer service life at room temperature, and single-component packaging can be realized instead of A/B two-component packaging.
In patent CN111250169A, a platinum complex formed by using siloxane compounds containing unsaturated groups as ligands is used as a core and an active component, or an organic compound containing N, P is used as a modification aid to prepare a high-stability platinum complex catalyst, and the service life is only prolonged to 6-10 days. In the patent US6359098B1, cyclopentadiene, diyne and platinum are subjected to complex coordination to prepare the single-component platinum catalyst, and the prepared single-component addition type silicone rubber can be stored for only 80 days at room temperature and cannot meet the storage time requirement of the market on the single-component addition type silicone rubber.
Disclosure of Invention
In view of the above, the present invention aims to provide a single component platinum catalyst, a preparation method and an application thereof, wherein the catalyst is applied to addition type silicone rubber and has the advantages of long storage time and low initial vulcanization temperature.
The invention provides a single-component platinum catalyst, which comprises the following raw materials in parts by weight:
5-8 parts of chloroplatinic acid, 1-5 parts of alkyl thioether, 30-50 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, 10-20 parts of sodium bicarbonate, 90-150 parts of absolute ethyl alcohol and 0.5-1 part of adsorbent.
In the present invention, the sodium bicarbonate is used to neutralize the hydrochloric acid generated after the chloroplatinic acid is complexed.
In the present invention, the alkyl sulfide is selected from one or more of diethyl disulfide, butyl ethyl disulfide, ethyl methyl disulfide, ethyl propyl disulfide, diethyl sulfide, divinyl sulfide, diethyl trisulfide and diethyl tetrasulfide.
In the present invention, the adsorbent is activated carbon;
the granularity of the activated carbon is 200-300 meshes;
the pH value of the activated carbon is 5-7.
The invention provides a preparation method of a single-component platinum catalyst in the technical scheme, which comprises the following steps:
mixing and heating alkyl thioether and part of absolute ethyl alcohol, dropwise adding a mixed solution of chloroplatinic acid and the rest of absolute ethyl alcohol, reacting after dropwise adding, adding sodium bicarbonate and 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, continuing to react, cooling, and filtering to obtain a filtrate;
and mixing the filtrate with an adsorbent, distilling to remove the solvent, and filtering again to obtain the platinum catalyst.
The preparation method provided by the invention uses alkyl thioether to be firstly complexed with platinum, and then vinyl double-end socket (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane) is complexed with platinum, so that the prepared single-component platinum is applied to addition type silicone rubber, and has the advantages of long operation time, low curing temperature and high reaction speed.
The absolute ethyl alcohol adopted when the alkyl thioether and the part of the absolute ethyl alcohol are mixed accounts for 20-40% of the total usage amount of the absolute ethyl alcohol.
In the invention, the reaction time is 1-2 h after the dropwise addition of the mixed solution of chloroplatinic acid and absolute ethyl alcohol, and the temperature is 50-70 ℃;
the continuous reaction time of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane after the addition is 1.5-3 h, and the temperature is 50-70 ℃.
The invention adopts a reduced pressure heating rotary distillation mode to remove the solvent; and filtering again to remove the active carbon to obtain the platinum catalyst. In the invention, the vacuum degree for distilling and removing the solvent is-0.08 to-0.1 MPa, and the temperature is 40 to 60 ℃.
The invention preferably washes the removed activated carbon with 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane.
The invention provides an application of a single-component platinum catalyst in preparation of addition type silicone rubber;
the single-component platinum catalyst is the platinum catalyst in the technical scheme or the platinum catalyst prepared by the preparation method in the technical scheme.
In the invention, the platinum catalyst accounts for 5-10 ppm of the mass of the addition type silicone rubber base rubber.
In the invention, the addition type silicone rubber is in a liquid state; the addition type silicone rubber-based rubber is preferably prepared according to the following method:
55-60 parts of vinyl-terminated silicone oil with the viscosity of 100000mPa.s, 7-9 parts of hexamethyldisilazane, 0.6-0.8 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane and 2.2-2.8 parts of deionized water are mixed, stirred at room temperature, then 26-30 parts of fumed silica are sequentially added, banburying is carried out, stirring is carried out under the vacuum condition, and cooling is carried out, so as to obtain the addition type silicone rubber base.
In the invention, the banburying temperature is 165-175 ℃, and the banburying time is 55-65 min; in the specific embodiment, the banburying temperature is 170 ℃ and the banburying time is 60 min.
In a specific embodiment of the present invention, the addition type silicone rubber-based adhesive is preferably prepared according to the following method:
58 parts of vinyl-terminated silicone oil with the viscosity of 100000mPa.s, 8 parts of hexamethyldisilazane, 0.7 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane and 2.5 parts of deionized water are mixed, stirred at room temperature, then 28 parts of fumed silica are sequentially added, banburying is carried out, stirring under the vacuum condition is carried out, and cooling is carried out, thus obtaining the addition type silicone rubber base.
The invention provides a single-component platinum catalyst, which comprises the following raw materials in parts by weight: 5-8 parts of chloroplatinic acid, 1-5 parts of alkyl thioether, 30-50 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, 10-20 parts of sodium bicarbonate, 90-150 parts of absolute ethyl alcohol and 0.5-1 part of adsorbent. The invention adopts alkyl thioether and 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane to carry out complexation with platinum, and the obtained platinum catalyst is applied to addition type silicone rubber, so that the addition type silicone rubber has low initial vulcanization temperature and long storage time. The experimental results show that: the initial vulcanization temperature of the addition type silicone rubber is 98-108 ℃, and the room temperature storage time is more than 230 h; the storage time at 50 ℃ is 58-71 days.
Drawings
FIG. 1 is an infrared spectrum of a platinum catalyst prepared in example 1 of the present invention.
Detailed Description
In order to further illustrate the present invention, a one-component platinum catalyst, a preparation method and an application thereof according to the present invention will be described in detail with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
1.83g of diethyl disulfide and 30g of absolute ethyl alcohol are put into a 250ml three-neck flask, the three-neck flask is put into a 60 ℃ water bath kettle, nitrogen is introduced, the three-neck flask is condensed and refluxed, mechanical stirring is started, 5.18g of chloroplatinic acid and 60g of absolute ethyl alcohol mixed solution are dripped, after dripping is finished within 0.5h, the constant temperature reaction is carried out for 1.7h, then 12.5g of sodium bicarbonate is added, after uniform stirring, 31g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane is added for constant temperature reaction for 2.5h, after cooling to room temperature, filtration is carried out, 0.5g of activated carbon is added into filtrate, rotary distillation is carried out under the conditions of-0.09 MPa and 50 ℃, the active carbon is removed by filtration of kettle liquid, and is washed by 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, and 9.71g of light yellow transparent liquid with 20 percent platinum content is obtained.
FIG. 1 is an infrared spectrum of a platinum catalyst prepared according to an example of the present invention; from the IR spectrum, 1254.3cm-1、1279.01cm-1Is a characteristic absorption peak of C-S of the alkyl sulfide, 786.72cm-1、839.7cm-1Is Si-CH3Characteristic absorption peak at 1008.64cm-1、1052.49cm-1Is a characteristic absorption peak of Si-O-Si, 1596.12cm-1Is Si-CH2＝CH3Characteristic absorption peak.
Example 2
1.55g of divinyl sulfide and 25g of absolute ethyl alcohol are put into a 250ml three-neck flask, the three-neck flask is put into a 55 ℃ water bath kettle, nitrogen is introduced, the three-neck flask is condensed and refluxed, mechanical stirring is started, a mixed solution of 6.21g of chloroplatinic acid and 80g of absolute ethyl alcohol is dripped, after dripping is completed within 0.6h, the constant temperature reaction is carried out for 2h, then 15g of sodium bicarbonate is added, after uniform stirring, 37g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane is added for constant temperature reaction for 3h, after cooling to room temperature, filtration is carried out, 0.7g of activated carbon is added into filtrate, rotary distillation is carried out under the conditions of-0.085 MPa and 60 ℃, activated carbon is removed through filtration of kettle liquid, the activated carbon is washed by 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, and 9.31g of light yellow transparent liquid with 25% platinum content is obtained.
Example 3
3.07g of ethyl propyl disulfide and 40g of absolute ethyl alcohol are put into a 250ml three-neck flask, the three-neck flask is placed in a 65 ℃ water bath kettle, nitrogen is introduced, the three-neck flask is condensed and refluxed, mechanical stirring is started, a mixed solution of 7.77g of chloroplatinic acid and 95g of absolute ethyl alcohol is dripped, after 0.8h of dripping is finished, the constant temperature reaction is carried out for 1.3h, then 19g of sodium bicarbonate is added, after uniform stirring is carried out, 46g of 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane is added for constant temperature reaction for 2h, after cooling to room temperature, filtration is carried out, 1g of activated carbon is added into filtrate, rotary distillation is carried out under the conditions of-0.085 MPa and 55 ℃, activated carbon is removed by filtration of kettle liquid, the activated carbon is washed by 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane, 16.19g of light yellow transparent liquid with 18% platinum content.
Example 4
3g of diethyl trisulfide and 35g of absolute ethyl alcohol are put into a 250ml three-neck flask, the three-neck flask is put into a 70 ℃ water bath kettle, nitrogen is introduced, the three-neck flask is condensed and refluxed, mechanical stirring is started, a mixed solution of 6.73g of chloroplatinic acid and 85g of absolute ethyl alcohol is dripped, after 0.6h of dripping is finished, the mixture is reacted for 1h at constant temperature, then 16g of sodium bicarbonate is added, after uniform stirring, 40g of 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane is added for constant temperature reaction for 1.5h, after cooling to room temperature, filtration is carried out, 0.8g of activated carbon is added into filtrate, rotary distillation is carried out under the conditions of-0.095 MPa and 50 ℃, active carbon is removed by filtration of kettle liquid, the activated carbon is washed by 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane, and 10.97g of light yellow transparent liquid with the platinum content of 23% is obtained.
Comparative example 1
A single component platinum catalyst was prepared according to the method of patent US6252028B 1. 0.5g of (1, 5-cyclooctadiene) platinum (II) dichloride [ PtCl ]2(COD)]Suspending in 30ml ethanol, cooling to 0 deg.C under nitrogen, slowly adding 0.27g phenylacetylene and sodium ethoxide solution (sodium 61.5mg, ethanol 10ml), reacting for about 50min, filtering the precipitate, and recrystallizing with dichloromethane. 0.614g of a platinum complex [ (COD) Pt (C.ident.C-Ph) is obtained2]。
Comparative example 2
A single component platinum catalyst was prepared according to the method of patent US6187890B 1. 0.4g of cis (triphenylphosphine) platinum (II) chloride, 0.15g of ethynylcyclohexanol, 0.019g of copper iodide and 20ml of diethylamine suspension were stirred for 10 minutes, and the mixture was then refluxed for 30 minutes. After cooling to room temperature, the precipitate was separated from the solution and washed with ethanol and recrystallized from dichloromethane or ethanol to give 0.406g of the product was tras- (Ph)3P)2Pt[-C≡CC6H10(OH)]2。
The catalysts obtained in examples and comparative examples were each prepared with toluene to obtain a catalyst having a platinum content of 0.5%.
58 parts of vinyl-terminated silicone oil with the viscosity of 100000mPa.s, 8 parts of hexamethyldisilazane, 0.7 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane and 2.5 parts of deionized water are put into an internal mixer, stirred at room temperature for 10 minutes and fully mixed uniformly, and 28 parts of 200m of deionized water are put into the internal mixer at room temperature2And uniformly stirring the silica white by the gas phase method, starting heating to raise the temperature to 170 ℃ for banburying for 60min, then starting vacuum, continuously stirring for 100min under the condition that the vacuum degree is minus 0.09MPa, and cooling to obtain the addition type liquid silicone rubber base rubber.
100g of the base rubber was taken, 5g of terminal vinyl silicone oil having a viscosity of 100000mPa.s and 3.5g of straight-chain type side hydrogen-containing silicone oil having a hydrogen content of 0.7% were added thereto, and the mixture was stirred uniformly, and then 0.2g of the catalyst having a platinum content of 0.5% obtained in examples and comparative examples, which was prepared from toluene, was added thereto, and the mixture was stirred uniformly. The onset of sulfidation temperature was measured using a high iron sulfur analyzer and the storage time at room temperature and 50 ℃ was measured and the results are shown in table 1.
TABLE 1 test results of examples and comparative examples
From the results, the single-component platinum catalyst provided by the invention is applied to addition type silicone rubber, the initial vulcanization temperature is low, the storage time at room temperature and 50 ℃ is long, and the preparation method is simple.
From the above examples, the invention provides a single-component platinum catalyst, and the preparation raw materials comprise the following components in parts by weight: 5-8 parts of chloroplatinic acid, 1-5 parts of alkyl thioether, 30-50 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, 10-20 parts of sodium bicarbonate, 90-150 parts of absolute ethyl alcohol and 0.5-1 part of adsorbent. The invention adopts alkyl thioether and 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane to carry out complexation with platinum, and the obtained platinum catalyst is applied to addition type silicone rubber, so that the addition type silicone rubber has low initial vulcanization temperature and long storage time. The experimental results show that: the initial vulcanization temperature of the addition type silicone rubber is 98-108 ℃, and the room temperature storage time is more than 230 h; the storage time at 50 ℃ is 58-71 days.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The single-component platinum catalyst comprises the following preparation raw materials in parts by weight:
5-8 parts of chloroplatinic acid, 1-5 parts of alkyl thioether, 30-50 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, 10-20 parts of sodium bicarbonate, 90-150 parts of absolute ethyl alcohol and 0.5-1 part of adsorbent.
2. The one-component platinum catalyst according to claim 1, wherein the alkyl sulfide is selected from one or more of diethyl disulfide, butyl ethyl disulfide, ethyl methyl disulfide, ethyl propyl disulfide, diethyl sulfide, divinyl sulfide, diethyl trisulfide and diethyl tetrasulfide.
3. The platinum catalyst according to claim 1, wherein the adsorbent is activated carbon;
the granularity of the activated carbon is 200-300 meshes;
the pH value of the activated carbon is 5-7.
4. A method for preparing the single component platinum catalyst of any one of claims 1 to 3, comprising the steps of:
mixing and heating alkyl thioether and part of absolute ethyl alcohol, dropwise adding a mixed solution of chloroplatinic acid and the rest of absolute ethyl alcohol, reacting after dropwise adding, adding sodium bicarbonate and 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, continuing to react, cooling, and filtering to obtain a filtrate;
and mixing the filtrate with an adsorbent, distilling to remove the solvent, and filtering again to obtain the platinum catalyst.
5. The method according to claim 4, wherein the reaction time after the dropwise addition of the mixed solution of chloroplatinic acid and absolute ethanol is 1-2 hours, and the temperature is 50-70 ℃;
the continuous reaction time of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane after the addition is 1.5-3 h, and the temperature is 50-70 ℃.
6. The method according to claim 4, wherein the solvent is distilled off at a vacuum degree of-0.08 to-0.1 MPa and a temperature of 40 to 60 ℃.
7. An application of a single-component platinum catalyst in the preparation of addition type silicone rubber;
the single-component platinum catalyst is the platinum catalyst as described in any one of claims 1 to 3 or the platinum catalyst prepared by the preparation method as described in any one of claims 4 to 6.
8. The use according to claim 7, wherein the platinum catalyst is present in an amount of 5 to 10ppm based on the mass of the addition silicone rubber-based paste.
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