Environment-friendly single-component bio-based polyurethane beautifying gel and preparation method thereof

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to environment-friendly single-component bio-based polyurethane beauty gel and a preparation method thereof.The environment-friendly single-component bio-based polyurethane beauty gel comprises, by weight, 100 parts of bio-based polyurethane prepolymer, 10-20 parts of a curing agent, 1-10 parts of a curing agent, 1-10 parts of a curing agent and 1-10 parts of a curing agent. 0.1 to 0.5 part of an anti-aging auxiliary agent; 10 to 20 parts of filler; 4-8 parts of a thixotropic agent; 1-5 parts of an adhesion promoter; 1-3 parts of a dispersant; 0.1 to 0.5 part of a defoaming agent and 0.2 to 0.8 part of a catalyst II. The adopted bio-based polyurethane prepolymer has renewability and environmental friendliness, multiple polyols are compounded to serve as a main body raw material, the bio-based content is increased, and meanwhile, the performance of a main body product of the beauty gel is not affected; compared with the traditional one-component polyurethane beauty gel, the beauty gel provided by the invention is green and environment-friendly while the performance of the beauty gel is ensured, the pressure on the environment is reduced, and the beauty gel is particularly suitable for scenes with high requirements on environmental protection and decoration.

Description

TECHNICAL FIELD

[0001] The present application relates to an environment-friendly single-component bio-based polyurethane cosmetic glue and a preparation method thereof, and belongs to the technical field of adhesives. BACKGROUND

[0002] As a sealing material for building decoration, cosmetic glue can be divided into three categories according to its chemical composition: silicone-based cosmetic glue, silane-modified polyether-based cosmetic glue, and polyurethane-based cosmetic glue. In particular, polyurethane-based cosmetic glue has excellent mechanical strength, anti-yellowing performance, and acid and alkali corrosion resistance, making it widely used in high-end decoration fields. In recent years, the market size of the building decoration industry has continued to grow, driving the demand for cosmetic glue to increase significantly. Among them, polyurethane cosmetic glue has a continuously increasing market share due to its outstanding environmental characteristics, such as low volatile organic compound (VOC) content, non-toxicity, and other advantages, and has become one of the mainstream products in this field.

[0003] However, the existing cosmetic glue still has the following technical problems: First, the dependence on petroleum-based raw materials is serious: traditional polyurethane cosmetic glue mainly relies on petroleum-based raw materials such as isocyanate and polyol, and the production process has high carbon emissions, which does not meet the green chemistry development trend.

[0004] Second, there is a risk of harmful substance release: some silicone-based cosmetic glue (such as ketone oxime type) may release butanone oxime (which has potential carcinogenicity), and some solvent-based cosmetic glue contains harmful volatile substances such as formaldehyde and benzene series, which affects indoor air quality and is difficult to meet the safety needs of sensitive scenarios.

[0005] Third, sustainability is insufficient: traditional petroleum-based materials are not renewable, and long-term dependence will exacerbate resource pressure, and the cost control is difficult due to the influence of crude oil price fluctuations.

[0006] Therefore, developing an environmentally friendly, non-harmful substance releasing, and sustainable development potential cosmetic glue product has become a technical problem to be solved in the field. SUMMARY

[0007] The present application provides an environmentally friendly single-component bio-based polyurethane cosmetic glue and a preparation method thereof to solve the above technical problems.

[0008] The technical solution of the present application to solve the above technical problems is as follows: One of the purposes of the present application is to provide an environmentally friendly single-component bio-based polyurethane cosmetic glue, which comprises the following components by weight: 100 parts of bio-based polyurethane prepolymer; 0.1-0.5 parts of anti-aging additive; 10-20 parts of filler; Thixotropic agent 5-8 parts Adhesion promoter 1-5 parts Dispersant 1-3 parts Defoaming agent 0.1-0.5 parts Catalyst two 0.2-0.8 parts.

[0009] The beneficial effects of the present application are that the bio-based polyurethane prepolymer used in the present application has renewability and environmental friendliness, and a variety of polyols are used as the main raw material to improve the bio-based content while maintaining the performance of the main product of the beauty glue; compared with the traditional single-component polyurethane beauty glue, the present application is more environmentally friendly while ensuring the performance of the beauty glue, which reduces the pressure on the environment, and is particularly suitable for scenes with high environmental and decorative requirements.

[0010] On the basis of the above technical scheme, the present application can also be improved as follows: Further, the raw materials of the bio-based polyurethane prepolymer include the following components by weight: Isocyanate 15-40 parts Polyether polyol or polyester polyol 0-30 parts Bio-based polyol 30-50 parts Plasticizer 5-20 parts Catalyst one 0.1-0.3 parts.

[0011] Further, the bio-based polyol is selected from at least one of soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, castor oil polyol, olive oil polyol, sugar polyol, bio-based glycerol, and bio-based ethylene glycol.

[0012] Further, the isocyanate is selected from at least one of 4,4'-diisocyanate dicyclohexyl methane, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-di(isocyanate methyl) cyclohexane, trimethyl hexamethylene diisocyanate, methylcyclohexyl diisocyanate, biuret triisocyanate, and hexamethylene diisocyanate trimer.

[0013] Further, the polyether polyol is selected from at least one of polypropylene oxide glycol, polytetrahydrofuran ether glycol, and oxirane-oxirane copolymer ether glycol.

[0014] Further, the polyester polyol is selected from at least one of adipic acid-based polyester diol, phthalic anhydride-based polyester diol, and epsilon-caprolactone-based polyester diol.

[0015] Further, the plasticizer is at least one of dioctyl adipate, dioctyl phthalate, diisooctyl phthalate, diisodecyl phthalate, diisononyl phthalate, dioctyl terephthalate.

[0016] Further, the catalyst one is at least one of organic tin catalyst, organic bismuth catalyst, amine catalyst.

[0017] Further, the preparation of the bio-based polyurethane prepolymer comprises the following steps: Step (1), the polyether polyol, polyester polyol and part of the bio-based polyol are dehydrated under vacuum at 100-120℃ to a moisture content of ≤0.05%; Step (2), under the protection of nitrogen, isocyanate and catalyst one are added, then the remaining bio-based polyol is added under stirring, and the reaction is carried out at 80-120℃ for 6-24 hours; Step (3), the plasticizer is added and stirring is continued for 20-50 minutes, and the product is sealed and stored.

[0018] Further, the anti-aging aid is at least one of benzotriazole, triazine, benzophenone, hindered phenol, phosphite.

[0019] Further, the thixotropic agent is at least one of fumed silica, polyamide wax, hydrogenated castor oil polyol.

[0020] Further, the adhesion promoter is at least one of silane coupling agent, titanate coupling agent, high molecular polyester, phosphate.

[0021] Further, the dispersant is at least one of polyurethane type dispersant, acrylate copolymer type dispersant, phosphate type dispersant.

[0022] Further, the filler is at least one of heavy calcium carbonate, light calcium carbonate, barium sulfate, kaolin, talc powder, diatomite, magnesium carbonate, silica powder, molecular sieve.

[0023] Further, the defoaming agent is at least one of silicone type defoaming agent, polyether modified silicone type defoaming agent.

[0024] Further, the catalyst two is selected from organic bismuth catalyst.

[0025] Further, it also includes 3-6 parts of color paste by weight, and the color paste is at least one of organic pigment color paste and inorganic pigment color paste.

[0026] The second object of the present application is to provide a preparation method of the above-mentioned environmentally friendly single-component bio-based polyurethane cosmetic glue, which specifically comprises the following steps: Step one, put the bio-based polyurethane prepolymer into the stirred tank, start stirring, the stirring speed is 80 RPM ~ 150 RPM; Step two: add dispersant, adhesion promoter and catalyst two, stir for 20 min ~ 40 min; Step three: add thixotropic agent and filler, stir for 20 min ~ 60 min; Step four: add color paste, anti-aging aid, defoaming agent, stir for 20 min ~ 40 min; Step five: vacuum, discharge and pack. DETAILED DESCRIPTION

[0027] The principles and characteristics of the present application are described below, and the examples are only used to explain the present application, not to limit the scope of the present application.

[0028] Example 1 (1) Preparation of bio-based polyurethane prepolymer: Reaction kettle preparation, the reaction kettle after drying treatment is replaced by nitrogen, ensure that there is no moisture and oxygen in the kettle, start the stirring device, set the stirring speed to 150 RPM.

[0029] Step one, add 20g PPG 5000 and 50g castor oil polyol to the reaction kettle, heat to 120℃ under vacuum conditions, stir for 3 hours to reduce the moisture content to below 0.05%.

[0030] Step two, accurately weigh 15g isophorone diisocyanate, 15g 4,4'-diisocyanate dicyclohexyl methane, 0.1g organic bismuth, and stir under nitrogen protection into the reaction kettle. Reaction at 100℃ for 12h.

[0031] Step three, accurately weigh 10g diisooctyl phthalate and add to the reaction kettle, stir for 30 min at 100℃.

[0032] Step four, discharge the bio-based polyurethane prepolymer to the storage container, keep the storage container sealed, and store it in a low temperature, dry environment.

[0033] (2) Preparation of environmentally friendly single-component bio-based polyurethane cosmetic glue: Step one, accurately weigh 8g molecular sieve, 4g fumed silica, 10g light calcium carbonate, and put them into an oven, dry at 120℃ for 24h for standby.

[0034] Step two, add 100g bio-based polyurethane prepolymer to the stirred tank, start stirring, and set the stirring speed to 120 RPM.

[0035] Step three, accurately weigh 2g BYK110, 3g KH560, 0.3g organic tin into the stirring kettle in turn, stir for 25min.

[0036] Step four, add fumed silica, molecular sieve and light calcium carbonate, stir for 30min.

[0037] Step five, accurately weigh 5g titanium white paste, 0.1g ECOSCINOX 1076, 0.1g ECOSCINOX 770, 0.1g silicone defoamer, stir for 30min.

[0038] Step six, vacuum, discharge and sub-pack.

[0039] Example 2 (1) Preparation of bio-based polyurethane prepolymer: Reaction kettle preparation, replace the reaction kettle after drying treatment with nitrogen, ensure that there is no moisture and oxygen in the kettle, start the stirring device, set the stirring speed to 150RPM.

[0040] Step one, add 15g WHP208 polyester polyol, 50g castor oil polyol into the reaction kettle, heat to 120℃ under vacuum condition, stir for 3 hours to reduce the moisture content to below 0.05%.

[0041] Step two, accurately weigh 15g 4,4'-diisocyanate dicyclohexyl methane, 20g MDI-50, 0.2g organic tin catalyst, stir and add to the reaction kettle under nitrogen protection, react at a reaction temperature of 80℃ for 12h.

[0042] Step three, accurately weigh 10g diisooctyl phthalate into the reaction kettle, stir for 30min at a reaction temperature of 100℃.

[0043] Step four, discharge the bio-based polyurethane prepolymer to the storage container, keep the storage container sealed, and store it in a low-temperature, dry environment.

[0044] (2) Preparation of single-component bio-based polyurethane cosmetic glue: Step one, accurately weigh 10g molecular sieve, 6g fumed silica, 10g light calcium carbonate, put them into an oven and dry at 120℃ for 24h for standby; Step two, add 100g bio-based polyurethane prepolymer into the stirring kettle, start stirring, and set the stirring speed to 120RPM.

[0045] Step three, accurately weigh 2g BYK2013, 3g KH560, 0.5g organic tin into the stirring kettle, stir for 25min.

[0046] Step four, add fumed silica, molecular sieve and light calcium carbonate in sequence, stir for 30 min.

[0047] Step five, accurately weigh 5 g titanium white paste, 0.1 g ECOSCINOX 1010, 0.1 g FENTASORB 531, 0.1 g silicone defoamer, stir for 30 min.

[0048] Step six, vacuumize, discharge and sub-pack.

[0049] Example 3 (1) Preparation of bio-based polyurethane prepolymer: Reaction kettle preparation, nitrogen replacement was carried out on the reaction kettle after drying treatment, to ensure that there was no moisture and oxygen in the kettle, the stirring device was turned on, and the stirring speed was set to 150 RPM.

[0050] Step one, add 25 g PPG 1000, 30 g castor oil polyol, and 10 g cashew nut shell oil polyol (LITE-9001) into the reaction kettle, heat to 120℃ under vacuum condition, and stir for 3 hours to reduce the moisture content to below 0.05%.

[0051] Step two, accurately weigh 25 g 4,4'-diisocyanate dicyclohexyl methane, 10 g isophorone diisocyanate, and 0.1 g organotin catalyst into the reaction kettle, and react at a reaction temperature of 80℃ for 12 h.

[0052] Step three, accurately weigh 15 g diisooctyl phthalate and add it to the reaction kettle, and stir at a reaction temperature of 100℃ for 30 min.

[0053] Step four, discharge the bio-based polyurethane prepolymer to the storage container, keep the storage container sealed, and store it in a low-temperature, dry environment.

[0054] (2) Preparation of single-component bio-based polyurethane cosmetic glue: Step one, accurately weigh 10 g molecular sieve, 5 g fumed silica, and 10 g silicon powder, and place them in an oven for drying at 120℃ for 24 h for standby.

[0055] Step two, add 100 g bio-based polyurethane prepolymer into the stirring kettle, turn on the stirring, and set the stirring speed to 120 RPM.

[0056] Step three, accurately weigh 2 g BYK2013, 3 g KH560, and 0.5 g organotin into the stirring kettle, and stir for 25 min. Step four, add fumed silica, molecular sieve and silicon powder in sequence, and stir for 30 min.

[0057] Step five, accurately weigh 5 g titanium white paste, 0.1 g ECOSCINOX 1010, 0.1 g FENTASORB 531, 0.1 g silicone defoamer, stir for 30 min.

[0058] Step six, vacuumize, discharge and sub-pack.

[0059] Performance test 1. Surface dry time test: the above examples 1-3 and single-component polyurethane cosmetic glue (commercially available) were tested for surface dry time, and the test method was carried out according to GB / T 1728-2020 "Paint film, putty film drying time determination method", and the specific values are shown in Table 1.

[0060] 2. Sag degree test according to GB / T 13477.6, place in (50±2℃) oven for 24 h.

[0061] 3. Volatile organic compounds (VOC) content test according to the provisions of GB18583.

[0062] 4. Extrudability test according to the provisions of GB / T 13477.3, nozzle inner diameter 4 mm, air pressure adjusted to (300±10) kPa, sample pretreatment temperature (23±2)℃.

[0063] 5. Mildew resistance test according to the provisions of GB / T 1741. The cosmetic glue for indoor decoration and decoration was prepared to form a coating layer with a thickness of about 2 mm under standard test conditions and cured for 7 d. No carrier panel was used during the test, and a test piece with a size of 50 mm x 50 mm was cut directly for testing.

[0064] 6. Tensile bonding according to GB / T 13477.10, bonding after cold drawing-hot pressing according to GB / T 13477.13, and tensile bonding after immersion according to GB / T 13477.11.

[0065] The test results of the above performance tests are shown in Table 1.

[0066] Table 1 Performance test results

[0067] From the performance data results of the examples and the comparative examples (one-component polyurethane cosmetic glue) in Table 1, it can be seen that the one-component bio-based cosmetic glue is prepared by using the bio-based polyurethane prepolymer as a raw material, the product is compared with the traditional one-component polyurethane cosmetic glue, while ensuring the original performance, the raw material is taken from renewable resources, which is more green and environmentally friendly, and reduces the pressure on the environment, and is especially suitable for scenes with high requirements for environmental protection and decoration. The performance of the one-component bio-based cosmetic glue described in the application is closely related to the raw materials and process parameters, and if any raw material or process parameter is changed, the performance of the cosmetic glue may be reduced.

[0068] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An environmentally friendly one-component bio-based polyurethane cosmetic glue, characterized in that, By weight parts, including the following components: Bio-based polyurethane prepolymer 100 parts; Anti-aging aids 0.1-0.5 parts; Filler 10-20 parts; Thixotropic agent 4-8 parts; Adhesion promoter 1-5 parts; Dispersing agent 1-3 parts; Defoaming agent 0.1-0.5 parts; Catalyst two 0.2-0.8 parts.

2. The environmentally friendly one-component bio-based polyurethane cosmetic glue according to claim 1, characterized in that, By weight parts, the raw materials of the bio-based polyurethane prepolymer include the following components: Isocyanate 15-40 parts; Polyether polyol or polyester polyol 0-30 parts; Bio-based polyol 30-50 parts; Plasticizer 5-20 parts; Catalyst one 0.1-0.3 parts.

3. The environmentally friendly one-component bio-based polyurethane cosmetic glue according to claim 2, characterized in that, The bio-based polyol is selected from at least one of soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, castor oil polyol, olive oil polyol, sugar polyol, bio-based glycerol, and bio-based ethylene glycol.

4. The environmentally friendly single-component bio-based polyurethane cosmetic glue according to claim 2, characterized in that, The isocyanate is selected from at least one of 4,4'-diisocyanate dicyclohexyl methane, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanate methyl) cyclohexane, trimethyl hexamethylene diisocyanate, methyl cyclohexyl diisocyanate, biuret triisocyanate, and hexamethylene diisocyanate trimer; The polyether polyol is selected from at least one of polypropylene oxide glycol, polytetrahydrofuran ether glycol, and oxirane-oxirane copolymer ether glycol. The polyester polyol is selected from at least one of adipic acid-based polyester diol, phthalic anhydride-based polyester diol, and ε-caprolactone-based polyester diol.

5. The environmentally friendly single-component bio-based polyurethane cosmetic glue according to claim 2, characterized in that, The plasticizer is selected from at least one of adipic acid dioctyl ester, phthalic acid dioctyl ester, phthalic acid diisooctyl ester, phthalic acid diisodecyl ester, phthalic acid diisononyl ester, and terephthalic acid dioctyl ester; The catalyst one is selected from at least one of organic tin catalyst, organic bismuth catalyst, and amine catalyst.

6. The environmentally friendly one-component bio-based polyurethane cosmetic glue according to any one of claims 2-5, characterized in that, The preparation of the bio-based polyurethane prepolymer includes the following steps: Step (1), dehydrate the polyether polyol, polyester polyol, and part of the bio-based polyol under vacuum conditions at 100-120°C to a moisture content of ≤0.05%; Step (2), add isocyanate and catalyst one under nitrogen protection, then add the remaining bio-based polyol under stirring, and react at a temperature of 80-120°C for 6-24 hours; Step (3), add the plasticizer and continue stirring for 20-50 minutes, then discharge and seal for storage.

7. The environmentally friendly single-component bio-based polyurethane cosmetic glue according to claim 1, characterized in that, The anti-aging aids are selected from at least one of benzotriazole, triazine, benzophenone, hindered phenol, and phosphite ester; The thixotropic agent is selected from at least one of fumed silica, polyamide wax, and hydrogenated castor oil polyol; The adhesion promoter is selected from at least one of silane coupling agent, titanate coupling agent, high molecular polyester, and phosphate ester.

8. The environmentally friendly one-component bio-based polyurethane cosmetic glue according to claim 1, characterized in that, The dispersant is selected from at least one of polyurethane type dispersant, acrylate copolymer type dispersant, phosphate type dispersant; The filler is selected from at least one of heavy calcium carbonate, light calcium carbonate, barium sulfate, kaolin, talc, diatomite, magnesium carbonate, silica powder, molecular sieve; The defoaming agent is selected from at least one of silicone defoaming agent, polyether modified silicone defoaming agent; The catalyst two is selected from at least one of organic bismuth catalyst or organic tin catalyst. 9.The environmentally friendly one-component bio-based polyurethane cosmetic glue according to claim 1, characterized in that, The color paste is selected from at least one of organic pigment color paste, inorganic pigment color paste.

10. A process for preparing an environmentally friendly one-component bio-based polyurethane cosmetic glue according to any one of claims 1-9, characterized in that, Specifically comprising the following steps: Step one, put the bio-based polyurethane prepolymer into the stirred tank, start stirring, the stirring speed is 80 RPM-150 RPM; Step two: add dispersant, adhesion promoter and catalyst two, stir for 20 min-40 min; Step three: add thixotropic agent and filler, stir for 20 min-60 min; Step four: add color paste, anti-aging additive, defoaming agent, stir for 20 min-40 min; Step five: vacuum, discharge and package.

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