CN115819715A - Gel ice pad polyurethane stock solution, preparation method thereof and gel ice pad - Google Patents
Gel ice pad polyurethane stock solution, preparation method thereof and gel ice pad Download PDFInfo
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- CN115819715A CN115819715A CN202310108153.7A CN202310108153A CN115819715A CN 115819715 A CN115819715 A CN 115819715A CN 202310108153 A CN202310108153 A CN 202310108153A CN 115819715 A CN115819715 A CN 115819715A
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Abstract
The invention provides a gel ice pad polyurethane stock solution, a preparation method thereof and a gel ice pad, wherein the gel ice pad polyurethane stock solution comprises a component A and a component B, the preparation raw materials of the component A comprise ethylene oxide-tetrahydrofuran copolyether, polyether polyol, a chain extender, a plasticizer A, a water absorbent and a catalyst A, and the component B is a product of a prepolymerization reaction of isocyanate, polyester polyol and the plasticizer B. The gel ice pad prepared from the gel ice pad polyurethane stock solution provided by the invention has the characteristics of high specific heat capacity and small compression permanent deformation.
Description
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to a gel ice pad polyurethane stock solution, a preparation method thereof and a gel ice pad.
Background
The cooling ice pad is a practical cooling product in summer and is generally applied to the production and living environment of people. The cooling material selected in the manufacturing process of part of ice pad products in the market at present is hydrosol or ice crystal sand, which can generate form change after absorbing heat, changes from solid state into liquid and has certain fluidity, so that the cooling material needs to be packaged by materials such as polyvinyl chloride and the like to prevent the liquid from flowing out. The production process of the ice pad product is complicated, potential safety hazards such as liquid leakage exist, hydrosol or ice crystal sand have no elasticity, and the prepared ice pad product has the problem of poor comfort degree in the use process. The other part of the ice pad product is prepared from polyurethane, the polyurethane ice pad has better strength and toughness, is simple and convenient to prepare, but has the problems of low specific heat capacity, poor cool feeling and easy collapse and deformation after long-term use.
Therefore, it is necessary to develop a polyurethane material which is easy and convenient to produce, has good cool feeling and is not easy to deform after long-term use so as to meet the performance requirements of the gel ice pad.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the gel ice pad polyurethane stock solution, the preparation method thereof and the gel ice pad.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a gel ice pad polyurethane stock solution, which comprises a component A and a component B, wherein the preparation raw materials of the component A comprise ethylene oxide-tetrahydrofuran copolyether, polyether polyol, a chain extender, a plasticizer A, a water absorbent and a catalyst A, and the component B is a product of a prepolymerization reaction of isocyanate, polyester polyol and a plasticizer B.
The gel ice pad polyurethane stock solution is prepared by matching ethylene oxide-tetrahydrofuran copolyether, polyether glycol, a chain extender, a plasticizer A, a water absorbent, a catalyst A, isocyanate, polyester polyol and a plasticizer B, and the components generate mutual synergistic action, so that the specific heat capacity of the gel ice pad is effectively improved, the heat absorption capacity is improved, the mechanical property is improved, and the compression permanent deformation is reduced.
The ethylene oxide-tetrahydrofuran copolyether is randomly copolymerized ethylene oxide-tetrahydrofuran copolyether, tetrahydrofuran chain segments are uniformly dispersed in the whole structure of the ethylene oxide-tetrahydrofuran copolyether chain segments, and the ethylene oxide-tetrahydrofuran copolyether has low viscosity and low crystallinity. The ethylene oxide-tetrahydrofuran copolyether can be uniformly dispersed in the gel ice pad polyurethane stock solution, the compression set degree of the gel ice pad is reduced, and meanwhile, the ethylene oxide-tetrahydrofuran copolyether can form a synergistic effect with other components, so that the specific heat capacity is improved.
Preferably, the preparation method of the ethylene oxide-tetrahydrofuran copolyether comprises the following steps: tetrahydrofuran and ethylene oxide are used as raw materials, micromolecular dihydric alcohol is used as an initiator, lewis acid is used as a catalyst, and ethylene oxide-tetrahydrofuran copolyether is obtained through cationic active polymerization reaction.
Preferably, the molar ratio of tetrahydrofuran and ethylene oxide is 1 to 1.
Preferably, the temperature of the polymerization reaction is-10 ℃ to 10 ℃ (e.g., -10 ℃, -8 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃,0 ℃,1 ℃, 2 ℃, 3 ℃,4 ℃,5 ℃, 8 ℃ or 10 ℃, etc.), more preferably-5 ℃ to 5 ℃, and the reaction time is 5h to 10h (e.g., 5h, 5.5h, 6h, 6.2h, 6.5h, 6.8h, 7h, 7.2h, 7.5h, 8h, 9h, 9.5h or 10h, etc.), more preferably 6h to 8h.
Preferably, the ethylene oxide-tetrahydrofuran copolyether has a hydroxyl value of 30 to 150mgKOH/g, such as 30mgKOH/g, 50mgKOH/g, 70mgKOH/g, 90mgKOH/g, 100mgKOH/g, 110mgKOH/g, 120mgKOH/g, 130mgKOH/g, 140mgKOH/g, 150mgKOH/g, and the like.
In the present invention, the ethylene oxide-tetrahydrofuran copolyether preferably has a hydroxyl value of 30 to 150mgKOH/g because: the ethylene oxide-tetrahydrofuran copolyether with the hydroxyl value less than 30mgKOH/g has high viscosity and is not beneficial to processing; the degree of compression set of the obtained gel ice pad is increased and the elasticity is reduced by the ethylene oxide-tetrahydrofuran copolyether with the hydroxyl value of more than 150 mgKOH/g.
Preferably, the polyether polyol is selected from polyethylene glycol polyether, preferably any one of PEG-200, PEG-500 or PEG-1000 or a combination of at least two thereof.
In the present invention, the polyethylene glycol polyether is preferred because: the polyethylene glycol polyether contains a large number of hydroxyl groups, can form a large number of hydrogen bond structures, can form a synergistic effect with other components, and improves the specific heat capacity of the gel ice pad.
Preferably, the chain extender is selected from any one of 3, 5-diethyltoluenediamine, 1, 2-propylenediamine, N-methyldiethanolamine or isophoronediamine or a combination of at least two thereof.
Preferably, the plasticizer a is selected from any one of dibutyl adipate, dimethyl adipate or diisopropyl adipate or a combination of at least two of the dibutyl adipate, the dimethyl adipate and the diisopropyl adipate.
Preferably, the water absorbent is selected from any one of sodium polyacrylate, potassium polyacrylate or polyvinyl alcohol acrylic acid copolymer or the combination of at least two of the sodium polyacrylate, the potassium polyacrylate or the polyvinyl alcohol acrylic acid copolymer.
In the invention, the water absorbent plays a very good role in absorbing water in the prepared gel ice pad, and after absorbing a certain amount of water in the using process, the water absorbent can form a synergistic effect with other components, so that the specific heat capacity of the gel ice pad is further improved.
Preferably, the catalyst A is selected from any one of or a combination of at least two of the non-foaming catalysts Niax D-22, dabco T-9 or Dabco T-12.
Preferably, the isocyanate is selected from any one of hexamethylene diisocyanate, isophorone diisocyanate, 4-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate or naphthalene diisocyanate or a combination of at least two of the hexamethylene diisocyanate, the isophorone diisocyanate, the carbodiimide-modified diphenylmethane diisocyanate or the naphthalene diisocyanate.
Preferably, the polyester polyol is selected from any one of or a combination of at least two of a polyester polyol of a polyacylate series or a polyester polyol of a terephthalic acid series.
Preferably, the polyester polyol has a number average molecular weight of 1000 to 3000, for example 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000 or the like.
In the present invention, the number average molecular weight of the polyester polyol is preferably 1000 to 3000 because: the number average molecular weight of the polyester polyol is more than 3000, the viscosity of the polyester polyol is very high, and the processing is not facilitated; less than 1000, the elasticity of the prepared gel ice pad is obviously reduced, and the compression permanent deformation degree is increased.
Preferably, the plasticizer B is any one of dioctyl adipate, dibutyl sebacate or diisononyl phthalate or a combination of at least two of the dioctyl adipate, the dibutyl sebacate and the diisononyl phthalate.
Preferably, the component A of the gel ice pad polyurethane stock solution comprises the following components in parts by weight:
40-80 parts of ethylene oxide-tetrahydrofuran copolyether
10-50 parts of polyether polyol
10-50 parts of plasticizer A
2-20 parts of chain extender
Catalyst A0.1-2.0 parts
0.5-2.0 parts of water absorbent.
The weight portion of the ethylene oxide-tetrahydrofuran copolyether in the component A of the gel ice pad polyurethane stock solution is 40-80 parts, such as 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts.
The weight portion of the polyether polyol in the component A of the gel ice pad polyurethane stock solution is 10-50 parts, such as 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.
The weight portion of the plasticizer A in the component A of the gel ice pad polyurethane stock solution is 10-50 parts, such as 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.
The weight portion of the chain extender in the component A of the gel ice pad polyurethane stock solution is 2-20 parts, such as 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts or 20 parts.
The weight portion of the catalyst A in the component A of the gel ice pad polyurethane stock solution is 0.1-2.0 parts, such as 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1.0 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.7 parts, 1.9 parts or 2.0 parts and the like.
The weight portion of the water absorbent in the component A of the gel ice pad polyurethane stock solution is 0.5-2.0 parts, such as 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8 or 2.0.
Preferably, the component B of the gel ice pad polyurethane stock solution comprises the following components in parts by weight:
10-30 parts of isocyanate
20-80 parts of polyester polyol
20-80 parts of a plasticizer B.
The weight portion of the isocyanate in the component B of the gel ice pad polyurethane stock solution is 10-30 parts, such as 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts or 30 parts.
The weight portion of the polyester polyol in the component B of the gel ice pad polyurethane stock solution is 20-80 parts, such as 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts or 80 parts.
The weight portion of the plasticizer B in the component B of the gel ice pad polyurethane stock solution is 20-80 parts, such as 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts or 80 parts.
Preferably, the a component further comprises 0.3 to 2.5 (e.g., 0.3, 0.5, 0.7, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.3, or 2.5, etc.) parts by weight of a foam stabilizer; the foam stabilizer is selected from any one or the combination of at least two of ORTEGOL 215, DABCO LK 221, TEGOSTAB B8950 or DABCO DC 5000.
Preferably, the isocyanate, the polyester polyol and the plasticizer B of the B component further comprise adding a side reaction inhibitor to the system when performing the prepolymerization reaction, wherein the side reaction inhibitor is contained in the B component in an amount of from 10ppm to 200ppm (for example, 10ppm, 30ppm, 50ppm, 70ppm, 90ppm, 100ppm, 120ppm, 140ppm, 160ppm, 180ppm, 190ppm or 200ppm and the like), and the side reaction inhibitor is selected from any one or a combination of at least two of inorganic acid, organic acid or benzoyl chloride.
In a second aspect, the present invention provides a method for preparing a gel ice pad polyurethane stock solution as described in the first aspect, the method comprising the following steps:
(1) Preparation of component A: adding the preparation raw materials of the component A into a reactor, heating, uniformly mixing, cooling and discharging to obtain the component A.
(2) Preparation of the component B: adding polyester polyol, isocyanate and a plasticizer B into a reactor for prepolymerization reaction to obtain a component B.
Preferably, in the step (1), the temperature is raised to 50 to 80 ℃ (e.g., 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ and the like), and the cooling is cooled to 35 to 40 ℃ (e.g., 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃ and the like).
Preferably, in step (2), the temperature of the prepolymerization is 70-80 ℃ (e.g., 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃ and the like), and the reaction time is 2-3h (e.g., 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3h and the like).
In a third aspect, the invention provides a gel ice pad, which is prepared from the gel ice pad polyurethane stock solution of the first aspect.
Preferably, the method for preparing the gel ice pad by using the gel ice pad polyurethane stock solution of the first aspect is to mix the component a and the component B in a mass ratio of 100.
Compared with the prior art, the invention has the following beneficial effects:
in the gel ice mat polyurethane stock solution provided by the invention, the ethylene oxide-tetrahydrofuran copolyether, the polyether glycol, the chain extender, the plasticizer A, the water absorbent, the catalyst A, the isocyanate, the polyester polyol and the plasticizer B are compounded, so that the gel ice mat has high specific heat capacity, low compression permanent deformation, good cool feeling in use and difficult collapse and deformation after long-term use.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The starting materials used in the examples and comparative examples and their preparation were as follows:
ethylene oxide-tetrahydrofuran copolyether a prepared by the following method:
adding 500g of tetrahydrofuran, 500g of ethylene oxide, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate complex into a reaction vessel which is replaced by nitrogen respectively, reacting for 6h at the temperature of 0 ℃, vacuumizing to remove unreacted monomer micromolecules and water after the reaction is ended, dissolving a product by using toluene, filtering to remove the boron trifluoride diethyl etherate complex, and distilling the filtrate under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether a.
The hydroxyl value was measured according to GB/T12008.3-2009 to be 90mgKOH/g and the viscosity was measured according to GB/T12008.8-1992 to be 2000 mPas (40 ℃ C.).
Ethylene oxide-tetrahydrofuran copolyether b prepared by the following process:
adding 500g of tetrahydrofuran, 1000g of ethylene oxide, 75g of diethylene glycol and 0.8g of aluminum chloride-cyclohexanol complex into a reaction vessel which is replaced by nitrogen respectively, reacting for 6 hours at 10 ℃, vacuumizing to remove unreacted monomer micromolecules and water after the reaction is ended, dissolving a product by using toluene, filtering to remove the aluminum chloride-cyclohexanol complex, and distilling the filtrate under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether b.
The hydroxyl value was measured according to GB/T12008.3-2009 to be 56mgKOH/g and the viscosity was measured according to GB/T12008.8-1992 to be 3500 mPa. Multidot.S (40 ℃ C.).
Ethylene oxide-tetrahydrofuran copolyether c, prepared by the following process:
500g of tetrahydrofuran, 1200g of ethylene oxide, 145g of propylene glycol and 0.5g of niobium pentachloride complex are respectively added into a reaction vessel replaced by nitrogen, the reaction is carried out for 6h at the temperature of 5 ℃, after the reaction is ended, vacuum pumping is carried out to remove unreacted monomer micromolecules and water, toluene is used for dissolving the product, the niobium pentachloride complex is removed by filtration, and the filtrate is subjected to reduced pressure distillation to obtain the ethylene oxide-tetrahydrofuran copolyether c.
The hydroxyl value was measured according to GB/T12008.3-2009 to be 120mgKOH/g and the viscosity was measured according to GB/T12008.8-1992 to be 2100 mPa.S (40 ℃ C.).
Ethylene oxide-tetrahydrofuran copolyether d, prepared by the following process:
respectively adding 670g of tetrahydrofuran, 330g of ethylene oxide, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate complex into a reaction vessel replaced by nitrogen, reacting for 6h at-5 ℃, vacuumizing to remove unreacted monomer micromolecules and water after the reaction is ended, dissolving a product by using toluene, filtering to remove the boron trifluoride diethyl etherate complex, and distilling the filtrate under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether d.
The hydroxyl value was measured according to GB/T12008.3-2009 to be 90mgKOH/g and the viscosity was measured according to GB/T12008.8-1992 to be 1000 mPas (40 ℃ C.).
Ethylene oxide-tetrahydrofuran copolyether e prepared by the following process:
adding 220g of tetrahydrofuran, 780g of ethylene oxide, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate complex into a reaction vessel replaced by nitrogen respectively, reacting for 6h at 0 ℃, vacuumizing to remove unreacted monomer micromolecules and water after the reaction is ended, dissolving a product by using toluene, filtering to remove the boron trifluoride diethyl etherate complex, and distilling the filtrate under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether e.
The hydroxyl value was measured according to GB/T12008.3-2009 to be 90mgKOH/g and the viscosity was measured according to GB/T12008.8-1992 to be 10000 mPa. Multidot.S (40 ℃ C.).
Polytetrahydrofuran ether, prepared by the following method:
adding 1000g of tetrahydrofuran, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate into a reaction vessel which is replaced by nitrogen respectively, reacting for 6h at 0 ℃, vacuumizing to remove unreacted monomer micromolecules and water after the reaction is ended, dissolving a product by using toluene, filtering to remove the boron trifluoride diethyl etherate, and distilling the filtrate under reduced pressure to obtain the polytetrahydrofuran ether.
The hydroxyl value was measured according to GB/T12008.3-2009 to be 90mgKOH/g and the viscosity was measured according to GB/T12008.8-1992 to be 400 mPas (40 ℃ C.).
Polyethylene oxide ether, prepared by the following method:
1000g of ethylene oxide, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate are respectively added into a reaction vessel which is replaced by nitrogen, the mixture reacts for 6 hours at the temperature of 0 ℃, after the reaction is ended, the mixture is vacuumized to remove unreacted monomer micromolecules and water, toluene is used for dissolving products, the boron trifluoride diethyl etherate is filtered and removed, and the filtrate is subjected to reduced pressure distillation to obtain the polyethylene oxide ether.
The hydroxyl value was measured according to GB/T12008.3-2009 to be 90mgKOH/g and the viscosity was measured according to GB/T12008.8-1992 to be 100000 mPas (40 ℃ C.).
The polyester polyol a is prepared by the following method:
adding 1500g of adipic acid, 500g of ethylene glycol and 500g of butanediol into a reaction kettle in sequence, stirring, starting to heat, introducing nitrogen into the upper part of the reaction kettle, keeping the temperature constant for 1 hour when the temperature is raised to 135 ℃, continuing to heat, switching to introduce nitrogen from the lower part of the reaction liquid surface when the temperature is raised to 180 ℃, and gradually increasing the nitrogen quantity to strengthen dehydration. Heating to 225 ℃, keeping the temperature constant for 1 hour, adding 0.5g of tetrabutyl titanate, starting to vacuumize to-10 kpa, and carrying out ester exchange reaction for 4 hours to obtain the polyester polyol a.
The hydroxyl value was 56mgKOH/g and the number average molecular weight was 2000 as determined by HG/T2709-1995.
Polyester polyol b, prepared by the following method:
adding 1500g of adipic acid, 220g of ethylene glycol and 880g of diethylene glycol into a reaction kettle in sequence, stirring, starting heating, introducing nitrogen into the upper part of the reaction kettle, keeping the temperature constant for 1 hour when the temperature is raised to 135 ℃, continuing heating, switching to introduce nitrogen from the lower part of the reaction liquid surface when the temperature is raised to 180 ℃, and gradually increasing the nitrogen quantity to strengthen dehydration. Heating to 225 ℃, keeping the temperature constant for 1 hour, adding 0.5g of tetrabutyl titanate, starting to vacuumize to-10 kpa, and carrying out ester exchange reaction for 4 hours to obtain polyester polyol b.
The hydroxyl value was 62mgKOH/g and the number average molecular weight was 1800 as determined by HG/T2709-1995.
Polyester polyol c, prepared by the following method:
adding 1500g of adipic acid, 160g of ethylene glycol and 820g of diethylene glycol into a reaction kettle in sequence, opening and stirring, starting to heat, introducing nitrogen into the upper part of the reaction kettle, keeping the temperature constant for 1 hour when the temperature is raised to 140 ℃, continuing to heat, switching to introduce nitrogen from the lower part of the reaction liquid level when the temperature is raised to 180 ℃, and gradually increasing the nitrogen quantity to strengthen dehydration. Heating to 225 ℃, keeping the temperature constant for 1 hour, adding 0.5g of tetrabutyl titanate, starting to vacuumize to-10 kpa, and carrying out ester exchange reaction for 4 hours to obtain polyester polyol c.
The hydroxyl value was 56mgKOH/g and the number average molecular weight was 2000 as determined by HG/T2709-1995.
Other reagents are commercially available products unless otherwise specified.
Example 1
The embodiment provides a gel ice pad polyurethane stock solution and a preparation method thereof, wherein the gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method comprises the following steps:
the component A comprises:
50 parts of ethylene oxide-tetrahydrofuran copolyether a, 20 parts of polyether glycol (PEG-200), 30 parts of plasticizer A (dibutyl adipate), 2 parts of chain extender (3.5-diethyltoluenediamine), 0.6 part of catalyst A (Niax D-22), 0.4 part of foam stabilizer (ORTEGOL 215) and 1 part of water absorbent (sodium polyacrylate) are put into a reaction kettle, heated to 60 ℃, mixed and stirred for 2 hours, cooled to 40 ℃, discharged, sealed and stored.
And B component:
putting 10 parts of hexamethylene diisocyanate, 10 parts of carbodiimide modified diphenylmethane diisocyanate, 40 parts of polyester polyol a, 40 parts of plasticizer B (dioctyl adipate) and inorganic acid (phosphoric acid, the content of the phosphoric acid in the component B is 100 ppm) into a reaction kettle, heating to 75 ℃ under the protection of nitrogen, carrying out prepolymerization reaction for 2.5 hours, then cooling to 45 ℃, and sealing and storing, wherein the content of free-NCO is 6.2%.
Example 2
The embodiment provides a gel ice pad polyurethane stock solution and a preparation method thereof, wherein the gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method comprises the following steps:
preparation of a component A:
40 parts of ethylene oxide-tetrahydrofuran copolyether b, 41 parts of polyether polyol (PEG-500), 20 parts of plasticizer A (dimethyl adipate), 3 parts of chain extender (N-methyldiethanolamine), 0.3 part of catalyst A (Dabco T-9), 0.4 part of foam stabilizer (DABCO LK 221) and 1.2 parts of water absorbent (potassium polyacrylate) are put into a reaction kettle, heated to 60 ℃, mixed and stirred for 2 hours, cooled to 40 ℃, discharged, sealed and stored.
B, preparation of a component:
placing 10 parts of isophorone diisocyanate, 10 parts of carbodiimide modified diphenylmethane diisocyanate, 35 parts of polyester polyol B, 45 parts of plasticizer B (dibutyl sebacate) and benzoyl chloride (the content of B in the component B is 200 ppm) in a reaction kettle, heating to 75 ℃ under the protection of nitrogen, carrying out prepolymerization reaction for 2.5 hours, then cooling to 45 ℃, keeping the content of free-NCO at 5.0%, and sealing and storing.
Example 3
The embodiment provides a gel ice pad polyurethane stock solution and a preparation method thereof, wherein the gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method comprises the following steps:
preparation of a component A:
putting 60 parts of ethylene oxide-tetrahydrofuran copolyether c, 20 parts of polyether polyol (PEG-1000), 20 parts of plasticizer A (diisopropyl adipate), 4 parts of chain extender (isophorone diamine), 0.2 part of catalyst A (Dabco T-12), 0.3 part of foam stabilizer (TEGOSTAB B8950) and 2 parts of water absorbent (sodium polyacrylate) into a reaction kettle, heating to 60 ℃, mixing and stirring for 2 hours, cooling to 40 ℃, discharging, and sealing for storage.
B, preparation of a component:
5 parts of naphthalene diisocyanate, 15 parts of carbodiimide modified diphenylmethane diisocyanate, 25 parts of polyester polyol c, 40 parts of plasticizer B (diisononyl phthalate) and inorganic acid (phosphoric acid, the content of which in component B is 20 ppm) are put in a reaction kettle, heated to 75 ℃ under the protection of nitrogen, subjected to prepolymerization for 2.5 hours, then cooled to 45 ℃, and sealed for storage, wherein the content of free-NCO is 4.8%.
Example 4
The embodiment provides a gel ice pad polyurethane stock solution and a preparation method thereof, wherein the gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method comprises the following steps:
the component A comprises:
putting 50 parts of ethylene oxide-tetrahydrofuran copolyether D, 20 parts of polyether polyol (PEG-200), 30 parts of plasticizer A (dibutyl adipate), 2 parts of chain extender (3.5-diethyltoluenediamine), 0.6 part of catalyst A (Niax D-22), 0.4 part of foam stabilizer (ORTEGOL 215) and 1 part of water absorbent (sodium polyacrylate) into a reaction kettle, heating to 60 ℃, mixing and stirring for 2 hours, cooling to 40 ℃, discharging, sealing and storing.
And B component:
putting 10 parts of hexamethylene diisocyanate, 10 parts of carbodiimide modified diphenylmethane diisocyanate, 40 parts of polyester polyol a, 40 parts of plasticizer B (dioctyl adipate) and inorganic acid (phosphoric acid, the content of the phosphoric acid in the component B is 100 ppm) into a reaction kettle, heating to 75 ℃ under the protection of nitrogen, carrying out prepolymerization reaction for 2.5 hours, then cooling to 45 ℃, and sealing and storing, wherein the content of free-NCO is 6.2%.
Example 5
The embodiment provides a gel ice pad polyurethane stock solution and a preparation method thereof, wherein the gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method comprises the following steps:
the component A comprises:
putting 50 parts of ethylene oxide-tetrahydrofuran copolyether e, 20 parts of polyether polyol (PEG-200), 30 parts of plasticizer A (dibutyl adipate), 2 parts of chain extender (3.5-diethyl toluenediamine), 0.6 part of catalyst A (Niax D-22), 0.4 part of foam stabilizer (ORTEGOL 215) and 1 part of water absorbent (sodium polyacrylate) into a reaction kettle, heating to 60 ℃, mixing and stirring for 2 hours, cooling to 40 ℃, discharging, and storing in a sealed manner.
And B component:
putting 10 parts of hexamethylene diisocyanate, 10 parts of carbodiimide modified diphenylmethane diisocyanate, 40 parts of polyester polyol a, 40 parts of plasticizer B (dioctyl adipate) and inorganic acid (phosphoric acid, the content of the phosphoric acid in the component B is 100 ppm) into a reaction kettle, heating to 75 ℃ under the protection of nitrogen, carrying out prepolymerization for 2.5 hours, then cooling to 45 ℃, keeping the free-NCO content at 6.2%, and sealing for storage.
Comparative example 1
The comparative example provides a gel ice pad polyurethane stock solution and a method of making the same. The gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method is the same as that of the component A in example 1 except that the component A is not added with ethylene oxide-tetrahydrofuran copolyether a.
Comparative example 2
The comparative example provides a gel ice pad polyurethane stock solution and a method of making the same. The gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method is the same as that of the gel ice pad polyurethane stock solution in example 1, except that the component A is not added with polyether polyol (PEG-200).
Comparative example 3
The comparative example provides a gel ice pad polyurethane stock solution and a method of making the same. The gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method is the same as that of the component A in example 1 except that a water absorbent (sodium polyacrylate) is not added to the component A.
Comparative example 4
In this comparative example, a gel ice pad polyurethane stock solution and a method of making the same are provided. The gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method is the same as that of the component 1, except that ethylene oxide-tetrahydrofuran copolyether a in the component A is replaced by the same-quality polytetrahydrofuran ether.
Comparative example 5
The comparative example provides a gel ice pad polyurethane stock solution and a method of making the same. The gel ice pad polyurethane stock solution comprises a component A and a component B, and the preparation method is the same as that of the component 1 except that ethylene oxide-tetrahydrofuran copolyether a in the component A is replaced by polyethylene oxide ether with the same mass.
Application examples 1 to 5
A gel ice pad was prepared by the following method using the gel ice pad polyurethane stock solutions of examples 1 to 5, respectively.
Keeping the temperature of a charging bucket A and the charging bucket B of a low-pressure foaming machine at 25 ℃, fully mixing a component A and a component B of a gel ice pad polyurethane stock solution with the mass ratio of 100.
Application example 6
A gel ice pad was prepared by using the gel ice pad polyurethane stock solution obtained in example 1, according to the following method.
Keeping the temperature of a charging bucket A and the charging bucket B of a low-pressure foaming machine at 25 ℃, fully mixing a component A and a component B of a gel ice pad polyurethane stock solution with the mass ratio of 100.
Application example 7
A gel ice pad was prepared by using the gel ice pad polyurethane stock solution obtained in example 1, according to the following method.
Keeping the temperature of a charging bucket A and the charging bucket B of a low-pressure foaming machine at 25 ℃, fully mixing a component A and a component B of a gel ice pad polyurethane stock solution with a mass ratio of 100 to 45 by using the low-pressure foaming machine, injecting the mixture into a 45 ℃ gel ice pad mould for reaction for 4min for molding, demoulding, and curing at 25 ℃ for 12h to obtain the gel ice pad.
Comparative application examples 1 to 5
A gel ice pad is prepared by adopting the gel ice pad polyurethane stock solutions obtained in the comparative examples 1 to 5 according to the following method.
Keeping the temperature of a charging bucket A and the charging bucket B of a low-pressure foaming machine at 25 ℃, fully mixing a component A and a component B of a gel ice pad polyurethane stock solution with the mass ratio of 100.
Comparative application example 6
A gel ice pad was prepared by using the gel ice pad polyurethane stock solution obtained in example 1, according to the following method.
Keeping the temperature of a charging bucket A and the charging bucket B of a low-pressure foaming machine at 25 ℃, fully mixing a component A and a component B of a gel ice pad polyurethane stock solution with the mass ratio of 100.
Comparative application example 7
A gel ice pad was prepared by using the gel ice pad polyurethane stock solution obtained in example 1, according to the following method.
Keeping the temperature of a charging bucket A and the charging bucket B of a low-pressure foaming machine at 25 ℃, fully mixing a component A and a component B of a gel ice pad polyurethane stock solution with the mass ratio of 100.
Comparative application example 8
A gel ice pad is commercially available polyurethane gel ice pad from QIGAR products, inc.
The gel ice pads prepared in application examples 1 to 7 and comparative application examples 1 to 8 are subjected to compression set, specific heat capacity and use effect tests, and the test method comprises the following steps:
(1) Compression set test: according to GB/T7759.1-2015 "determination of compression set of vulcanizates or thermoplastic rubbers part 1: the gel ice pad was tested for compression set under normal and high temperature conditions.
(2) Specific heat capacity test: according to GB/T19466.4-2016 Plastic Differential Scanning Calorimetry (DSC) part 4: determination of specific heat capacity ", a gel ice pad was subjected to a specific heat capacity test.
(3) And (3) testing the use effect:
and (3) cool feeling test: the cooling sensation caused by the rapid loss of heat from the skin surface at the instant the skin is contacted with the gel ice pad below its temperature is compared and judged.
Long-term use deformation test: after the gel ice pad is continuously used for three months, whether the obvious deformation phenomenon exists or not is observed.
The results of the test are shown in table 1:
TABLE 1
Note: in Table 1, "-" indicates that the result was not measured.
As is clear from the data in Table 1, the gel ice pad of the present invention has a compression set of 10.5% or less, a specific heat capacity of 2600J/(kg. K) or more, a good cooling effect, and a long-term use effect without deformation.
As can be seen from the analysis of comparative application examples 1 to 3 and application example 1, the use effects of comparative application examples 1 to 3 were inferior to application example 1, the compression set and the specific heat capacity were reduced without adding ethylene oxide-tetrahydrofuran copolyether (comparative application example 1), the specific heat capacity was reduced without adding polyether polyol (comparative application example 2), and the specific heat capacity was reduced without adding a water absorbent (comparative application example 3). Therefore, in the invention, the compression permanent deformation of the gel ice pad is reduced by adding the ethylene oxide-tetrahydrofuran copolyether, and the specific heat capacity of the gel ice pad is improved by using the components such as the ethylene oxide-tetrahydrofuran copolyether, the polyether polyol and the water absorbent in a matching way.
Analysis and comparison of application examples 4 to 5 and application example 1 show that if polytetrahydrofuran ether (comparative example 4) or polyethylene oxide ether (comparative example 5) is used instead of ethylene oxide-tetrahydrofuran copolyether, the degree of compression permanent deformation of the prepared gel ice pad is increased, and the specific heat capacity is reduced, because polytetrahydrofuran ether has a regular structure and high crystallinity, polyethylene oxide ether has high viscosity and high crystallinity, is easy to form phase separation when being blended with other raw materials, is not beneficial to forming a hydrogen bond structure between soft and hard polyurethane segments, and is difficult to mutually cooperate with other raw materials in the gel ice pad to improve the specific heat capacity. In addition, polytetrahydrofuran ether and polyethylene oxide ether are not uniformly dispersed in the polyurethane stock solution, resulting in an increase in compression set of the gel ice pad prepared.
Analyzing and comparing application examples 6 to 7 with application example 1, wherein if the mass ratio of the component A to the component B is more than 100 (comparison application example 6), the gel ice pad polyurethane stock solution cannot be cured, and the product cannot be molded; if the mass ratio of the component A to the component B is less than 100 (comparative application example 7), the gel ice pad polyurethane stock solution cannot be cured, and the product is not molded. Therefore, the mass ratio of the component A to the component B of the gel ice pad polyurethane stock solution is controlled within a specific range, so that the prepared gel ice pad polyurethane stock solution has better curing and forming properties. Analysis and comparison of application examples 8 and 1 to 7 show that the gel ice pad prepared by the invention has small compression set, high specific heat capacity and better use effect.
In conclusion, the gel ice pad is compounded by adopting the ethylene oxide-tetrahydrofuran copolyether, the polyether polyol, the chain extender, the plasticizer A, the water absorbent, the catalyst A, the isocyanate, the polyester polyol and the plasticizer B, so that the specific heat capacity in the gel ice pad is effectively improved, and the compression permanent deformation is reduced.
The applicant states that the present invention is illustrated by the above examples to the gel ice pad polyurethane stock solution, the preparation method thereof and the gel ice pad, but the present invention is not limited by the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The gel ice pad polyurethane stock solution is characterized by comprising a component A and a component B, wherein the preparation raw materials of the component A comprise ethylene oxide-tetrahydrofuran copolyether, polyether polyol, a chain extender, a plasticizer A, a water absorbent and a catalyst A, and the component B is a prepolymerization reaction product of isocyanate, polyester polyol and the plasticizer B.
2. The gel ice pad polyurethane stock solution according to claim 1, wherein the preparation method of the ethylene oxide-tetrahydrofuran copolyether comprises the following steps: taking tetrahydrofuran and ethylene oxide as raw materials, taking micromolecular dihydric alcohol as an initiator, taking Lewis acid as a catalyst, and carrying out cationic active polymerization reaction to obtain ethylene oxide-tetrahydrofuran copolyether;
the molar ratio of the tetrahydrofuran to the ethylene oxide is 1 to 1, the small molecule diol is selected from any one or the combination of at least two of ethylene glycol, propylene glycol, diethylene glycol or butanediol, and the Lewis acid is selected from any one or the combination of at least two of boron trifluoride diethyl etherate complex, aluminum chloride-cyclohexanol complex, niobium pentachloride complex or lanthanide triflate;
the temperature of the polymerization reaction is-10 ℃ to 10 ℃, and the reaction time is 5h to 10h;
the hydroxyl value of the ethylene oxide-tetrahydrofuran copolyether is 30 to 150 mgKOH/g.
3. The gel ice pad polyurethane dope according to claim 1, wherein the polyether polyol is selected from the group consisting of polyethylene glycol polyether;
the chain extender is selected from any one or the combination of at least two of 3, 5-diethyltoluenediamine, 1, 2-propylenediamine, N-methyldiethanolamine or isophorone diamine;
the plasticizer A is selected from any one or a combination of at least two of dibutyl adipate, dimethyl adipate or diisopropyl adipate;
the water absorbent is selected from any one or the combination of at least two of sodium polyacrylate, potassium polyacrylate or polyvinyl alcohol acrylic acid copolymer;
the catalyst A is selected from any one or a combination of at least two of non-foaming catalysts Niax D-22, dabco T-9 or Dabco T-12.
4. The gel ice pad polyurethane stock solution according to claim 1, wherein the isocyanate is selected from any one of hexamethylene diisocyanate, isophorone diisocyanate, 4-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate or naphthalene diisocyanate, or a combination of at least two thereof;
the polyester polyol is selected from any one of or a combination of at least two of polyester polyol of a polyacylate series or polyester polyol of a terephthalic acid series;
the number average molecular weight of the polyester polyol is 1000 to 3000;
the plasticizer B is any one or the combination of at least two of dioctyl adipate, dibutyl sebacate or diisononyl phthalate.
5. The gel ice mat polyurethane stock solution of claim 1, wherein the component A comprises the following components in parts by weight:
40-80 parts of ethylene oxide-tetrahydrofuran copolyether
10-50 parts of polyether polyol
10-50 parts of plasticizer A
2-20 parts of chain extender
Catalyst A0.1-2.0 parts
0.5-2.0 parts of water absorbent;
the component B comprises the following components in parts by weight:
10-30 parts of isocyanate
20-80 parts of polyester polyol
20-80 parts of a plasticizer B.
6. The gel ice pad polyurethane stock solution of claim 1, wherein the a component further comprises 0.3-2.5 parts by weight of a foam stabilizer; the foam stabilizer is selected from any one or the combination of at least two of ORTEGOL 215, DABCO LK 221, TEGOSTAB B8950 or DABCO DC 5000.
7. The gel ice pad polyurethane stock solution of claim 1, wherein the isocyanate, the polyester polyol and the plasticizer B further comprise a side reaction inhibitor added into the system during the prepolymerization reaction, wherein the content of the side reaction inhibitor in the component B is 10ppm to 200ppm, and the side reaction inhibitor is selected from any one or a combination of at least two of inorganic acid, organic acid or benzoyl chloride.
8. A method for preparing a gel ice pad polyurethane dope according to any one of claims 1-7, characterized in that the method comprises the following steps:
(1) Preparation of component A: adding the preparation raw material of the component A into a reactor, heating, uniformly mixing, cooling and discharging to obtain a component A;
(2) Preparation of the component B: adding polyester polyol, isocyanate and a plasticizer B into a reactor for prepolymerization reaction to obtain a component B.
9. The method according to claim 8, wherein the temperature rise in the step (1) is a temperature rise to 50 to 80 ℃, and the cooling is a temperature decrease to 35 to 40 ℃;
the temperature of the prepolymerization reaction in the step (2) is 70-80 ℃, and the reaction time is 2-3 h.
10. A gel ice mat, which is prepared by using the gel ice mat polyurethane stock solution of any one of claims 1 to 7;
the method for preparing the gel ice pad by using the gel ice pad polyurethane stock solution as claimed in any one of claims 1 to 7 comprises the following steps of mixing the component A and the component B according to a mass ratio of 100 to 15-50, injecting the mixture into a mold for reaction and molding, and then demolding and curing to obtain the gel ice pad.
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Denomination of invention: Gel ice cushion polyurethane stock solution, its preparation method and gel ice cushion Effective date of registration: 20230810 Granted publication date: 20230502 Pledgee: Bank of Jiangsu Co.,Ltd. Suzhou Branch Pledgor: XUCHUAN CHEMICAL (SUZHOU) Co.,Ltd. Registration number: Y2023980051419 |