CN115819715B - Gel ice pad polyurethane stock solution and preparation method thereof, and gel ice pad - Google Patents
Gel ice pad polyurethane stock solution and preparation method thereof, and gel ice pad Download PDFInfo
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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 an A component and a B component, the preparation raw materials of the A component comprise ethylene oxide-tetrahydrofuran copolyether, polyether polyol, a chain extender, a plasticizer A, a water absorbent and a catalyst A, and the B component is a product of a prepolymerization reaction of isocyanate, polyester polyol and a 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 set.
Description
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to gel ice pad polyurethane stock solution and a preparation method thereof, and a gel ice pad.
Background
The cooling ice pad is a practical cooling product in summer and is widely applied to the production and living environments of people. The cooling materials selected in the production of partial ice pad products in the market at present are hydrosol or ice crystal sand, and form change can occur after the ice pad products absorb heat, and the ice pad products are changed from solid state into liquid, so that the ice pad products have certain fluidity, and therefore, the cooling materials are required to be packaged by polyvinyl chloride and other materials, and the liquid is prevented from flowing out. The ice pad product has the problems of complicated production process, potential safety hazards such as liquid leakage and the like, no elasticity of hydrosol or ice crystal sand, and poor comfort in the use process. The other part of ice pad products are prepared from polyurethane, the polyurethane ice pad has better strength and toughness, and the preparation is simple and convenient, but has the problems of low specific heat capacity, poor cooling feeling and easy collapse and deformation after long-term use.
Therefore, there is a need to develop a polyurethane material that is simple and convenient to produce, has a good cooling sensation, and is not easily deformed for 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 gel ice pad polyurethane stock solution, a preparation method thereof and a gel ice pad.
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 an A component and a B component, wherein the A component is prepared from ethylene oxide-tetrahydrofuran copolyether, polyether polyol, chain extender, plasticizer A, water absorbent and catalyst A, and the B component is the product of the prepolymerization reaction of isocyanate, polyester polyol and plasticizer B.
According to the gel ice pad polyurethane stock solution, through the cooperation of ethylene oxide-tetrahydrofuran copolyether, polyether polyol, a chain extender, a plasticizer A, a water absorbent, a catalyst A, isocyanate, polyester polyol and a plasticizer B, a mutual synergistic effect is generated among the components, 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 set is reduced.
The ethylene oxide-tetrahydrofuran copolyether is random copolymerized ethylene oxide-tetrahydrofuran copolyether, and tetrahydrofuran chain segments are uniformly dispersed in the whole ethylene oxide-tetrahydrofuran copolyether chain segment structure, so that 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, so that 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, and 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 the ethylene oxide-tetrahydrofuran copolyether is obtained through cationic active polymerization.
Preferably, the molar ratio of tetrahydrofuran to ethylene oxide is 1:1-1:4 (e.g., 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1:4, etc.), the small molecule diol is selected from any one or a combination of at least two of ethylene glycol, propylene glycol, diethylene glycol, or butanediol, and the lewis acid is selected from any one or a combination of at least two of boron trifluoride diethyl ether complex, aluminum chloride-cyclohexanol complex, niobium pentachloride complex, or triflate of a lanthanide.
Preferably, the polymerization reaction temperature 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 ℃ -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.), further preferably 6h to 8h.
Preferably, the hydroxyl value of the ethylene oxide-tetrahydrofuran copolyether is 30-150 mgKOH/g, for example 30mgKOH/g, 50mgKOH/g, 70mgKOH/g, 90mgKOH/g, 100mgKOH/g, 110mgKOH/g, 120mgKOH/g, 130mgKOH/g, 140mgKOH/g or 150mgKOH/g, etc.
In the present invention, it is preferable that the hydroxyl value of the ethylene oxide-tetrahydrofuran copolyether is 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 ethylene oxide-tetrahydrofuran copolyethers with hydroxyl value greater than 150mgKOH/g have greater compression set and lower elasticity.
Preferably, the polyether polyol is selected from polyethylene glycol polyethers, preferably any one or a combination of at least two of PEG-200, PEG-500 or PEG-1000.
In the present invention, polyethylene glycol polyether is preferable because: the polyethylene glycol polyether contains a large number of hydroxyl groups, can form a large number of hydrogen bond structures, can form 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 or a combination of at least two of 3, 5-diethyl toluene diamine, 1, 2-propane diamine, N-methyl diethanol amine or isophorone diamine.
Preferably, the plasticizer A is selected from any one or a combination of at least two of dibutyl adipate, dimethyl adipate or diisopropyl adipate.
Preferably, the water absorbing agent is selected from any one or a combination of at least two of sodium polyacrylate, potassium polyacrylate or polyvinyl alcohol acrylic acid copolymer.
In the invention, the water absorbing agent plays a very good role in absorbing water in the prepared gel ice pad, and after absorbing a certain amount of water in the use process, the water absorbing agent 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 or a combination of at least two of a non-foaming catalyst Niax D-22, dabco T-9 or Dabco T-12.
Preferably, the isocyanate is selected from any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate, 4-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate or naphthalene diisocyanate.
Preferably, the polyester polyol is selected from any one or a combination of at least two of a polyadipic polyester polyol or a terephthalic polyester polyol.
Preferably, the polyester polyol has a number average molecular weight of 1000 to 3000, for example 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800 or 3000.
In the present invention, the polyester polyol preferably has a number average molecular weight of 1000 to 3000, because: the number average molecular weight of the polyester polyol is more than 3000, and the viscosity of the polyester polyol is high, which is not beneficial to processing; the elasticity of the prepared gel ice pad is obviously reduced, and the compression set degree is increased when the gel ice pad is smaller than 1000.
Preferably, the plasticizer B is selected from any one or a combination of at least two of dioctyl adipate, dibutyl sebacate or diisononyl phthalate.
Preferably, the A component 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 A component of the gel ice pad polyurethane stock solution comprises 40-80 parts of ethylene oxide-tetrahydrofuran copolyethers, such as 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts, and the like.
The weight part of polyether polyol in the A component 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, and the like.
The weight part of the plasticizer A in the A component 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, etc.
The weight part of the chain extender in the A component 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, and the like.
The weight part 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 parts, 0.3 parts, 0.5 parts, 0.7 parts, 0.9 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.7 parts, 1.9 parts or 2.0 parts, etc.
The water absorbent in the A component of the gel ice pad polyurethane stock solution is 0.5-2.0 parts by weight, 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, etc.
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 plasticizer B.
The weight portion of isocyanate in the component B of the gel ice pad polyurethane stock solution is 10-30, for example 10, 12, 15, 18, 20, 23, 25, 28 or 30.
The weight portion of the polyester polyol in the component B of the gel ice pad polyurethane stock solution is 20-80, such as 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 or 80, etc.
The weight part 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 and the like.
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 homogenizing agent is selected from any one or the combination of at least two of ORTEGOL 215, DABCO LK 221, TEGOSTAB 8950 or DABCO DC 5000.
Preferably, the isocyanate, the polyester polyol and the plasticizer B of the component B further comprise adding a side reaction inhibitor to the system when the pre-polymerization reaction is carried out, wherein the content of the side reaction inhibitor in the component B is 10 ppm-200 ppm (such as 10ppm, 30ppm, 50ppm, 70ppm, 90ppm, 100ppm, 120ppm, 140ppm, 160ppm, 180ppm, 190ppm or 200ppm and the like), and the side reaction inhibitor is any one or a combination of at least two of inorganic acid, organic acid or benzoyl chloride.
In a second aspect, the invention provides a method for preparing the gel ice pad polyurethane stock solution according to the first aspect, wherein the method comprises the following steps:
(1) And (3) preparation of the component A: and (3) adding the preparation raw materials of the component A into a reactor, heating, uniformly mixing, cooling and discharging to obtain the component A.
(2) And (3) preparation of a component B: adding polyester polyol, isocyanate and plasticizer B into a reactor for prepolymerization reaction to obtain a component B.
Preferably, in step (1), the temperature is raised to 50-80 ℃ (e.g. 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, or 80 ℃, etc.), and the cooling is cooled to 35-40 ℃ (e.g. 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, or 40 ℃, etc.).
Preferably, in step (2), the temperature of the prepolymerization reaction is 70-80 ℃ (e.g. 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃, etc.), and the reaction time is 2-3 hours (e.g. 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours, etc.).
In a third aspect, the invention provides a gel ice pad, which is prepared from the gel ice pad polyurethane stock solution in the first aspect.
Preferably, the method for preparing the gel ice pad by using the gel ice pad polyurethane stock solution according to the first aspect includes mixing the component A and the component B according to a mass ratio of 100:15-50 (for example, 100:15, 100:20, 100:25, 100:30, 100:35, 100:40, 100:45 or 100:50, etc.), injecting into a mold for reaction molding, demolding, and curing to obtain the gel ice pad.
Compared with the prior art, the invention has the following beneficial effects:
in the gel ice pad polyurethane stock solution provided by the invention, the ethylene oxide-tetrahydrofuran copolyether, polyether polyol, chain extender, plasticizer A, water absorbent, catalyst A, isocyanate, polyester polyol and plasticizer B are compounded, so that the gel ice pad has high specific heat capacity, low compression set, good cooling feeling during use and is not easy to collapse and deform after long-term use.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw materials used in each of the examples and comparative examples and their preparation are as follows:
ethylene oxide-tetrahydrofuran copolyether a was 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 into a reaction vessel replaced by nitrogen, reacting for 6 hours at 0 ℃, vacuumizing after the reaction is stopped to remove unreacted monomer micromolecules and water, using toluene dissolution products, filtering to remove the boron trifluoride diethyl etherate, and distilling the filtrate under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether a.
The hydroxyl value was 90mgKOH/g according to GB/T12008.3-2009 and the viscosity was 2000 mPa.S (40 ℃ C.) according to GB/T12008.8-1992.
Ethylene oxide-tetrahydrofuran copolyether b, prepared by the following method:
adding 500g of tetrahydrofuran, 1000g of ethylene oxide, 75g of diethylene glycol and 0.8g of aluminum chloride-cyclohexanol complex into a reaction vessel replaced by nitrogen, reacting for 6 hours at 10 ℃, vacuumizing after the reaction is stopped to remove unreacted monomer micromolecules and water, using toluene dissolution product, 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 56mgKOH/g according to GB/T12008.3-2009 and the viscosity was 3500 mPa.S (40 ℃ C.) according to GB/T12008.8-1992.
Ethylene oxide-tetrahydrofuran copolyether c, prepared by the following method:
adding 500g of tetrahydrofuran, 1200g of ethylene oxide, 145g of propylene glycol and 0.5g of niobium pentachloride complex into a reaction vessel replaced by nitrogen, reacting for 6 hours at 5 ℃, vacuumizing after the reaction is stopped to remove unreacted monomer micromolecules and water, using toluene dissolution product, filtering to remove the niobium pentachloride complex, and distilling the filtrate under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether c.
The hydroxyl value was 120mgKOH/g as measured in accordance with GB/T12008.3-2009 and the viscosity was 2100 mPa.S (40 ℃ C.) as measured in accordance with GB/T12008.8-1992.
Ethylene oxide-tetrahydrofuran copolyether d, prepared by the following method:
670g of tetrahydrofuran, 330g of ethylene oxide, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate are respectively added into a reaction vessel replaced by nitrogen, the reaction is carried out for 6 hours at the temperature of minus 5 ℃, unreacted monomer micromolecules and water are removed by vacuumizing after the reaction is stopped, toluene dissolution products are used, the boron trifluoride diethyl etherate is removed by filtration, and the filtrate is distilled under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether d.
The hydroxyl value was 90mgKOH/g according to GB/T12008.3-2009 and the viscosity was 1000 mPa.S (40 ℃ C.) according to GB/T12008.8-1992.
Ethylene oxide-tetrahydrofuran copolyether e, prepared by the following method:
220g of tetrahydrofuran, 780g of ethylene oxide, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate are respectively added into a reaction vessel replaced by nitrogen, the reaction is carried out for 6 hours at the temperature of 0 ℃, unreacted monomer micromolecules and water are removed by vacuumizing after the reaction is stopped, toluene dissolution products are used, the boron trifluoride diethyl etherate is removed by filtration, and the filtrate is distilled under reduced pressure to obtain the ethylene oxide-tetrahydrofuran copolyether e.
The hydroxyl value was 90mgKOH/g according to GB/T12008.3-2009 and the viscosity was 10000 mPa.S (40 ℃ C.) according to GB/T12008.8-1992.
Polytetrahydrofuran ether, prepared by the following method:
1000g of tetrahydrofuran, 50g of ethylene glycol and 0.5g of boron trifluoride diethyl etherate are respectively added into a reaction vessel replaced by nitrogen, the reaction is carried out for 6 hours at the temperature of 0 ℃, the unreacted monomer micromolecules and water are removed by vacuumizing after the reaction is stopped, toluene dissolution products are used, the boron trifluoride diethyl etherate is removed by filtration, and the polytetrahydrofuranate is obtained after the filtrate is distilled under reduced pressure.
The hydroxyl value was 90mgKOH/g according to GB/T12008.3-2009 and the viscosity was 400 mPa.S (40 ℃ C.) according to GB/T12008.8-1992.
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 replaced by nitrogen, the reaction is carried out for 6 hours at the temperature of 0 ℃, the unreacted monomer micromolecules and water are removed by vacuumizing after the reaction is stopped, toluene dissolution products are used, the boron trifluoride diethyl etherate is removed by filtration, and the filtrate is distilled under reduced pressure to obtain polyethylene oxide ether.
The hydroxyl value was 90mgKOH/g as measured according to GB/T12008.3-2009, and the viscosity 100000 mPa.S (40 ℃ C.) as measured according to GB/T12008.8-1992.
Polyester polyol a, prepared by the following method:
1500g of adipic acid, 500g of ethylene glycol and 500g of butanediol are sequentially added into a reaction kettle, stirring is carried out, heating is started, nitrogen is introduced into the upper part of the reaction kettle, heating is continued after the temperature is kept constant for 1 hour when the temperature is raised to 135 ℃, nitrogen is switched to be introduced from the lower part of the reaction liquid level when the temperature is raised to 180 ℃, and the nitrogen amount is gradually increased to strengthen dehydration. Heating to 225 ℃ to keep the temperature for 1 hour, adding 0.5g of tetrabutyl titanate, starting vacuumizing to-10 kpa, and carrying out transesterification for 4 hours to obtain the polyester polyol a.
The hydroxyl value was measured to be 56mgKOH/g according to the HG/T2709-1995 method and the number average molecular weight was 2000.
Polyester polyol b, prepared by the following method:
1500g of adipic acid, 220g of ethylene glycol and 880g of diethylene glycol are sequentially added into a reaction kettle, stirring is carried out, heating is started, nitrogen is introduced into the upper part of the reaction kettle, the temperature is kept constant for 1 hour when the temperature is raised to 135 ℃, heating is continued, nitrogen is switched to be introduced from the lower part of the reaction liquid level when the temperature is raised to 180 ℃, and the nitrogen amount is gradually increased to strengthen dehydration. Heating to 225 ℃ to keep the temperature for 1 hour, adding 0.5g of tetrabutyl titanate, starting vacuumizing to-10 kpa, and carrying out transesterification for 4 hours to obtain the polyester polyol b.
The hydroxyl value was measured to be 62mgKOH/g according to the HG/T2709-1995 method and the number average molecular weight was 1800.
Polyester polyol c, prepared by the following method:
1500g of adipic acid, 160g of ethylene glycol and 820g of diethylene glycol are sequentially added into a reaction kettle, stirring is started, heating is started, nitrogen is introduced into the upper part of the reaction kettle, the temperature is kept constant for 1 hour when the temperature is raised to 140 ℃, heating is continued, nitrogen is switched to be introduced from the lower part of the reaction liquid level when the temperature is raised to 180 ℃, and the nitrogen amount is gradually increased to strengthen dehydration. Heating to 225 ℃ to keep the temperature for 1 hour, adding 0.5g of tetrabutyl titanate, starting vacuumizing to-10 kpa, and carrying out transesterification for 4 hours to obtain the polyester polyol c.
The hydroxyl value was measured to be 56mgKOH/g according to the HG/T2709-1995 method and the number average molecular weight was 2000.
Other reagents, unless otherwise specified, are commercially available and commonly used.
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:
and (3) a component A:
50 parts of ethylene oxide-tetrahydrofuran copolyether a, 20 parts of polyether polyol (PEG-200), 30 parts of plasticizer A (dibutyl adipate), 2 parts of chain extender (3.5-diethyl toluene diamine), 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 ℃ and discharged, and sealed and stored.
And the component B comprises the following components:
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 which in the component B is 100 ppm) are placed in a reaction kettle, the temperature is raised to 75 ℃ under the protection of nitrogen, the prepolymerization reaction is carried out for 2.5 hours, then the temperature is reduced to 45 ℃, the free-NCO content is 6.2%, and the sealing and the preservation are carried out.
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:
and (3) preparing 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 ℃ and discharged, and sealed and stored.
And (2) preparing a component B:
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 which in the component B is 200 ppm) are placed in a reaction kettle, the temperature is raised to 75 ℃ under the protection of nitrogen, the prepolymerization reaction is carried out for 2.5 hours, then the temperature is reduced to 45 ℃, the free-NCO content is 5.0%, and the sealing and the preservation are carried out.
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:
and (3) preparing a component A:
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) are put into a reaction kettle, mixed and stirred for 2 hours after the temperature is raised to 60 ℃, discharged after the temperature is cooled to 40 ℃, and sealed and stored.
And (2) preparing a component B:
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 the component B is 20 ppm) are placed in a reaction kettle, heated to 75 ℃ under the protection of nitrogen, subjected to prepolymerization reaction for 2.5 hours, cooled to 45 ℃, and sealed and stored, wherein the free-NCO content 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:
and (3) a component A:
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-diethyl toluene diamine), 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 ℃ and discharged, and sealed and stored.
And the component B comprises the following components:
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 which in the component B is 100 ppm) are placed in a reaction kettle, the temperature is raised to 75 ℃ under the protection of nitrogen, the prepolymerization reaction is carried out for 2.5 hours, then the temperature is reduced to 45 ℃, the free-NCO content is 6.2%, and the sealing and the preservation are carried out.
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:
and (3) a component A:
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 toluene diamine), 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 ℃ and discharged, and sealed and stored.
And the component B comprises the following components:
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 which in the component B is 100 ppm) are placed in a reaction kettle, the temperature is raised to 75 ℃ under the protection of nitrogen, the prepolymerization reaction is carried out for 2.5 hours, then the temperature is reduced to 45 ℃, the free-NCO content is 6.2%, and the sealing and the preservation are carried out.
Comparative example 1
In the comparative example, a gel ice pad polyurethane stock solution and a preparation method thereof 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 embodiment 1, except that the component A is not added with ethylene oxide-tetrahydrofuran copolyether a.
Comparative example 2
In the comparative example, a gel ice pad polyurethane stock solution and a preparation method thereof are provided. The gel ice pad polyurethane stock solution includes an A-component and a B-component, which are prepared in the same manner as in example 1, except that the A-component is not a polyether polyol (PEG-200).
Comparative example 3
In the comparative example, a gel ice pad polyurethane stock solution and a preparation method thereof are provided. The gel ice pad polyurethane stock solution comprises an A component and a B component, and the preparation method is the same as that of the example 1, except that the A component is not added with water absorbent (sodium polyacrylate).
Comparative example 4
In the comparative example, a gel ice pad polyurethane stock solution and a preparation method thereof are provided. The gel ice pad polyurethane stock solution comprises a component A and a component B, which are prepared by the same method as in example 1, except that ethylene oxide-tetrahydrofuran copolyether a in the component A is replaced by polytetrahydrofuran ether of the same quality.
Comparative example 5
In the comparative example, a gel ice pad polyurethane stock solution and a preparation method thereof are provided. The gel ice pad polyurethane stock solution comprises a component A and a component B, which are prepared by the same method as in example 1, except that ethylene oxide-tetrahydrofuran copolyether a in the component A is replaced by polyethylene oxide ether of the same quality.
Application examples 1 to 5
The gel ice pad is prepared from the gel ice pad polyurethane stock solutions of examples 1-5 according to the following method.
Maintaining the temperature of a material tank A and a material tank B of a low-pressure foaming machine at 25 ℃, fully mixing the component A and the component B of the gel ice pad polyurethane stock solution with the mass ratio of 100:30 by the low-pressure foaming machine, injecting the mixture into a gel ice pad mold at 45 ℃ for reaction for 4min, forming, demolding, curing for 12h at 25 ℃, and obtaining the gel ice pad.
Application example 6
A gel ice pad is prepared by using the gel ice pad polyurethane stock solution obtained in the example 1 according to the following method.
Maintaining the temperature of a material tank A and a material tank B of a low-pressure foaming machine at 25 ℃, fully mixing the component A and the component B of the gel ice pad polyurethane stock solution with the mass ratio of 100:18 by the low-pressure foaming machine, injecting the mixture into a gel ice pad mold at 45 ℃ for reaction for 4min, forming, demolding, and curing for 12h at 25 ℃ to obtain the gel ice pad.
Application example 7
A gel ice pad is prepared by using the gel ice pad polyurethane stock solution obtained in the example 1 according to the following method.
Maintaining the temperature of a material tank A and a material tank B of a low-pressure foaming machine at 25 ℃, fully mixing the component A and the component B of the gel ice pad polyurethane stock solution with the mass ratio of 100:45 by the low-pressure foaming machine, injecting the mixture into a gel ice pad mold at 45 ℃ for reaction for 4min, forming, demolding, and curing for 12h at 25 ℃ to obtain the gel ice pad.
Comparative application examples 1 to 5
The gel ice pad is prepared from the gel ice pad polyurethane stock solutions obtained in comparative examples 1-5 according to the following method.
Maintaining the temperature of a material tank A and a material tank B of a low-pressure foaming machine at 25 ℃, fully mixing the component A and the component B of the gel ice pad polyurethane stock solution with the mass ratio of 100:30 by the low-pressure foaming machine, injecting the mixture into a gel ice pad mold at 45 ℃ for reaction for 4min, forming, demolding, and curing for 12h at 25 ℃ to obtain the gel ice pad.
Comparative application example 6
A gel ice pad is prepared by using the gel ice pad polyurethane stock solution obtained in the example 1 according to the following method.
Maintaining the temperature of a material tank A and a material tank B of a low-pressure foaming machine at 25 ℃, fully mixing the component A and the component B of the gel ice pad polyurethane stock solution with the mass ratio of 100:10 by the low-pressure foaming machine, injecting the mixture into a gel ice pad mold at 45 ℃ for reaction for 4min, forming, demolding, and curing for 12h at 25 ℃ to obtain the gel ice pad.
Comparative application example 7
A gel ice pad is prepared by using the gel ice pad polyurethane stock solution obtained in the example 1 according to the following method.
Maintaining the temperature of a material tank A and a material tank B of a low-pressure foaming machine at 25 ℃, fully mixing the component A and the component B of the gel ice pad polyurethane stock solution with the mass ratio of 100:60 by the low-pressure foaming machine, injecting the mixture into a gel ice pad mold at 45 ℃ for reaction for 4min, forming, demolding, and curing for 12h at 25 ℃ to obtain the gel ice pad.
Comparative application example 8
A gel ice pad, which is a commercially available polyurethane gel ice pad, available from cheddar products limited.
The gel ice pads prepared in application examples 1 to 7 and comparative application examples 1 to 8 were subjected to compression set, specific heat capacity and use effect tests, and the test methods were as follows:
(1) Compression set test: determination of compression set of vulcanizates or thermoplastic rubbers according to GB/T7759.1-2015 part 1: the gel ice pad was tested for compression set at normal and high temperatures.
(2) Specific heat capacity test: according to GB/T19466.4-2016 Plastic Differential Scanning Calorimetry (DSC) part 4: determination of specific heat capacity (determination of specific heat capacity) the gel ice pads were subjected to specific heat capacity tests.
(3) And (3) testing using effect:
and (3) cooling sense test: the cooling sensation formed by the rapid loss of heat from the surface of the skin is compared and judged according to the moment when the skin is contacted with the gel ice pad at a temperature lower than the temperature of the skin.
Long-term use deformation test: after the gel ice pad is continuously used for three months, whether the gel ice pad has obvious deformation phenomenon is observed.
The results of the test are shown in table 1:
TABLE 1
Note that: in table 1, "-" represents that the result was not measured.
As can be seen 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, and has a good cooling effect and a long-term use effect without deformation.
As can be seen from the analysis of comparative examples 1 to 3 and example 1, comparative examples 1 to 3 are inferior in use effect to example 1, and compression set and specific heat capacity decrease are not added to the ethylene oxide-tetrahydrofuran copolyether (comparative example 1), specific heat capacity decrease is not added to the polyether polyol (comparative example 2), and specific heat capacity decrease is not added to the water absorbing agent (comparative example 3). Therefore, in the invention, the compression set 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 the matched use of the components such as the ethylene oxide-tetrahydrofuran copolyether, the polyether polyol, the water absorbent and the like.
As can be seen from analysis and comparison of application examples 4-5 and application example 1, if polytetrahydrofuran ether (comparative example 4) or polyethylene oxide ether (comparative example 5) is used to replace ethylene oxide-tetrahydrofuran copolyether, the compression set degree of the prepared gel ice pad is increased, and the specific heat capacity is reduced, because the polytetrahydrofuran ether has strong structural regularity and crystallinity, the polyethylene oxide ether has strong viscosity and crystallinity, and is easy to form phase separation when being blended with other raw materials, the polyurethane ice pad is unfavorable for forming hydrogen bond structures among polyurethane soft and hard segments, and the specific heat capacity is difficult to be improved by mutual cooperation with other raw materials in the gel ice pad. In addition, polytetrahydrofuran ether and polyethylene oxide ether are unevenly dispersed in the polyurethane stock solution, so that the compression set of the prepared gel ice pad is increased.
As can be seen from the analysis of comparative examples 6 to 7 and example 1, if the mass ratio of the component A to the component B is greater than 100:15-50 (comparative example 6), the gel ice pad polyurethane stock solution cannot be cured, and the product is not formed; if the mass ratio of the component A to the component B is less than 100:15-50 (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, and the prepared gel ice pad polyurethane stock solution has good curing and forming properties. As can be seen from analysis and comparison of application examples 8 and application examples 1-7, the gel ice pad prepared by the method disclosed by the invention has the advantages of small compression set, high specific heat capacity and better use effect.
In summary, the specific heat capacity in the gel ice pad is effectively improved and the compression set is reduced 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 for compounding.
The applicant states that the gel ice pad polyurethane stock solution, the preparation method thereof and the gel ice pad of the invention are described by the above examples, but the invention is not limited to the above examples, i.e. the invention must not be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (9)
1. The gel ice pad polyurethane stock solution is characterized by comprising an A component and a B component, wherein the A component is prepared from ethylene oxide-tetrahydrofuran copolyether, polyether polyol, a chain extender, a plasticizer A, a water absorbent and a catalyst A, and the B component is a product of a prepolymerization reaction of isocyanate, polyester polyol and a plasticizer B;
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, and taking Lewis acid as a catalyst, and carrying out cationic active polymerization reaction to obtain ethylene oxide-tetrahydrofuran copolyether;
the hydroxyl value of the ethylene oxide-tetrahydrofuran copolyether is 30-150 mgKOH/g;
the ethylene oxide-tetrahydrofuran copolyether is a random copolymerized ethylene oxide-tetrahydrofuran copolyether;
the polyether polyol is selected from polyethylene glycol polyether;
the water absorbent is selected from any one or a combination of at least two of sodium polyacrylate, potassium polyacrylate or polyvinyl alcohol acrylic acid copolymer;
the number average molecular weight of the polyester polyol is 1000-3000;
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 plasticizer B;
the mass ratio of the component A to the component B is 100:15-50.
2. The gel ice-pad polyurethane stock solution according to claim 1, wherein the molar ratio of tetrahydrofuran to ethylene oxide is 1:1-1:4, the small molecule dihydric alcohol is selected from any one or a combination of at least two of ethylene glycol, propylene glycol, diethylene glycol or butanediol, and the lewis acid is selected from any one or a combination of at least two of boron trifluoride diethyl ether complex, aluminum chloride-cyclohexanol complex, niobium pentachloride complex or trifluoromethanesulfonate of lanthanide;
the temperature of the polymerization reaction is-10 ℃, and the reaction time is 5-10 hours.
3. The gel ice pad polyurethane stock solution according to claim 1, wherein the chain extender is selected from any one or a combination of at least two of 3, 5-diethyltoluenediamine, 1, 2-propylenediamine, N-methyldiethanolamine or isophoronediamine;
the plasticizer A is selected from any one or a combination of at least two of dibutyl adipate, dimethyl adipate and diisopropyl adipate;
the catalyst A is selected from any one or a combination of at least two of a non-foaming catalyst 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 or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate, 4-diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate or naphthalene diisocyanate;
the polyester polyol is selected from any one or a combination of at least two of a poly (adipic acid) polyester polyol and a terephthalic acid polyester polyol;
the plasticizer B is selected from any one or a combination of at least two of dioctyl adipate, dibutyl sebacate or diisononyl phthalate.
5. 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 homogenizing agent is selected from any one or the combination of at least two of ORTEGOL 215, DABCO LK 221, TEGOSTAB 8950 or DABCO DC 5000.
6. The gel ice pad polyurethane stock solution according to claim 1, wherein the isocyanate, the polyester polyol and the plasticizer B further comprise adding a side reaction inhibitor to the system when the pre-polymerization reaction is performed, wherein the content of the side reaction inhibitor in the component B is 10ppm to 200ppm, and the side reaction inhibitor is any one or a combination of at least two of inorganic acid, organic acid and benzoyl chloride.
7. The method for preparing a gel ice pad polyurethane stock solution according to any one of claims 1 to 6, wherein the method comprises the steps of:
(1) And (3) preparation of the 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) And (3) preparation of a component B: adding polyester polyol, isocyanate and plasticizer B into a reactor for prepolymerization reaction to obtain a component B.
8. The method of claim 7, wherein the heating in step (1) is to 50-80 ℃ and the cooling is to 35-40 ℃;
the temperature of the prepolymerization reaction in the step (2) is 70-80 ℃, and the reaction time is 2-3 h.
9. A gel ice pad, characterized in that the gel ice pad is prepared by using the gel ice pad polyurethane stock solution according to any one of claims 1-7;
the method for preparing the gel ice pad by using the gel ice pad polyurethane stock solution disclosed in any one of claims 1-6 comprises the steps of mixing the component A and the component B according to the mass ratio of 100:15-50, injecting into a mould for reaction 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 |