CN110591337A - High-performance TPU (thermoplastic polyurethane) film for glass interlayer and preparation method thereof - Google Patents
High-performance TPU (thermoplastic polyurethane) film for glass interlayer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a high-performance TPU film for a glass interlayer and a preparation method thereof. The high-performance TPU film for the glass interlayer is prepared from the following raw materials in percentage by mass: 75-90% of TPU master batch, 5-20% of polycarbonate, 0.1-0.5% of modified carbon nanofiber, 1-5% of modified cobalt oxide nanoparticle and 0.1-0.5% of antioxidant. The high-performance TPU film for the glass interlayer has high ultraviolet absorptivity, excellent toughness and light transmittance, low-temperature embrittlement temperature of-50 ℃, good mechanics, antistatic property and rebound resilience, excellent stability in the production process and wide application in the field of glass interlayer films; the invention also provides an efficient and stable preparation method.
Description
Technical Field
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a high-performance TPU film for a glass interlayer and a preparation method thereof.
Background
TPU is an environment-friendly high-molecular polymer with excellent performance, has the characteristics of elasticity of rubber and hardness of plastic, excellent thermodynamic property, light transmittance, wear resistance, resilience, easiness in processing and the like, and is widely applied to the fields of food, medical treatment, electronics, shoe materials, clothing and the like. With the increasing market demand of the modern glass assembly industry, the application of TPU thin films in glass interlayers is also increasing, at present, building glass and automobile interlayers are mainly PVB, EVA and SGP materials, wherein the EVA film layer is weak in ultraviolet resistance, and the SGP cost is high, so that the application of the TPU thin films is limited. Compared with PVB materials, the TPU high-performance film can be effectively combined with a PC plate (organic glass) to be used as bulletproof glass and smash-proof glass. Meanwhile, the TPU film has extremely high strength and penetration resistance which is 5-10 times of that of a PVB film, and can be effectively applied to bullet-proof glass of banks and anti-smashing glass of villas. The TPU structure endows the material with extremely high toughness, and is different from the characteristic of high brittleness of a PVB film. The TPU film is excellent in cold resistance, aging resistance and weather resistance, and cannot react with other materials, the ultraviolet-resistant TPU film can reduce ultraviolet rays to the maximum extent, and can shield over 99% of ultraviolet short-wave light irradiation, so that the TPU film is favorable for avoiding damage caused by ultraviolet radiation, and is a high-tech environment-friendly material. With the increasing requirements of people, the TPU thin film for the glass interlayer is increasingly applied to the fields of railways, spaceflight, buildings, electronic screens, military industry and the like, so that the development of the high-performance TPU thin film for the glass interlayer is very important.
CN2016103439679 discloses an antistatic TPU film, which comprises 70-90 weight parts of TPU particles and 20-40 weight parts of epoxy resin, and its preparation method and applicationPreparing the TPU film by 30-40 parts by weight of conductive carbon fiber and 5-10 parts by weight of antioxidant, and enabling the surface resistivity of the TPU film to be 8 multiplied by 10 through the synergistic effect among the components5-5×l06Omega, good antistatic performance.
Patent CN2018106030352 discloses a high-performance TPU modified film and a preparation method thereof, wherein the modified film comprises the following raw materials in parts by weight: 75 parts of TPU particles, 10 parts of rubber, 2 parts of sodium potassium silicate, 3 parts of flame retardant, 6 parts of natural polyphenol, 15 parts of epoxy resin, 12 parts of polyester short fiber, 6 parts of flatting agent, 10 parts of friction-resisting agent, 2 parts of environment-friendly plasticizer, 7 parts of photodegradation agent and 12 parts of starch. The modified TPU film has the advantages of high productivity, high surface gloss and the like, and also has excellent functions of high waterproofness, wear resistance, moisture permeability, wind resistance, cold resistance, antibiosis, mildew resistance, warm keeping, ultraviolet resistance and the like.
Although the above TPU film is improved in some properties, it has poor low-temperature toughness and cannot be applied to the field of glass interlayer films.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-performance TPU film for a glass interlayer, which has high ultraviolet absorptivity, excellent toughness and light transmittance performance, low-temperature embrittlement temperature of-50 ℃, good mechanics, antistatic property and rebound resilience, excellent stability in the production process and wide application in the field of glass interlayer films; the invention also provides an efficient and stable preparation method.
The invention relates to a high-performance TPU film for a glass interlayer, which is prepared from the following raw materials in percentage by mass:
the number average molecular weight of the polycarbonate was 6000-.
The modified carbon nanofiber is prepared by oxidizing carbon nanofiber with concentrated acid and performing silanization modification with a silane coupling agent, and the specific preparation method comprises the following steps:
(1) oxidation treatment: ultrasonically dispersing carbon nano-carbon fibers, heating, sequentially adding concentrated sulfuric acid and concentrated nitric acid, carrying out oxidation reaction, and carrying out post-treatment after the reaction is finished to obtain oxidized carbon nano-fibers; the feeding ratio of the carbon nanofibers to the concentrated sulfuric acid to the concentrated nitric acid is 3-5: 75-85: 35-45, wherein the carbon nano tube is measured by g, and the concentrated sulfuric acid and the concentrated nitric acid are measured by mL; the temperature of the oxidation reaction is 50-60 ℃, and the reaction time is 90-110 min;
(2) silanization modification: mixing the carbon nano-fiber subjected to oxidation treatment with a silane coupling agent, absolute ethyl alcohol and deionized water, performing ultrasonic dispersion for 15min, heating for silanization reaction, and introducing N in the whole process2Finally, washing with absolute ethyl alcohol and carrying out suction filtration treatment to obtain modified carbon nanofibers; wherein the feeding ratio of the carbon nano fiber subjected to oxidation treatment, the silane coupling agent, the anhydrous ethanol and the deionized water is 3: 0.4-0.5: 42-48: 14-16, wherein the oxidized carbon nanotube is counted by g, and the silane coupling agent (KH570), the absolute ethyl alcohol and the deionized water are counted by mL; the temperature of the silanization reaction is 65-75 ℃, and the reaction time is 120-140 min;
the modified nano cobalt oxide is prepared by performing silanization modification on nano cobalt oxide by a silane coupling agent, the particle size of the modified nano cobalt oxide is 300-400nm, and the preparation method comprises the following steps:
mixing nano cobalt oxide, a silane coupling agent, absolute ethyl alcohol and deionized water, performing ultrasonic dispersion for 15min, heating for silanization reaction, and introducing N in the whole process2Finally, freeze drying to obtain modified nano cobalt oxide; the feed ratio of the nano cobalt oxide to the KH-570 to the absolute ethyl alcohol to the deionized water is 3: 0.5-1: 40-45: 10-15, wherein the nano cobalt oxide is counted by g, and the silane coupling agent (KH570), the absolute ethyl alcohol and the deionized water are counted by mL; the temperature of the silanization reaction is 65-75 ℃, and the reaction time is 120-140 min.
The antioxidant is one or more of hindered phenol, hindered amine and phosphite antioxidant.
The TPU master batch is prepared from the following raw materials in percentage by mass and a catalyst:
the dosage of the catalyst is 0.005-0.03% of the total mass of the raw materials.
The oligomeric diol is one or more of polyoxyethylene diol, polyoxypropylene diol, polycaprolactone diol and polybutylene adipate diol, and has the number average molecular weight of 800-.
The diisocyanate is HMDI or HDI.
The chain extender is one or more of 1, 4-butanediol, 1, 2-propanediol, 1, 3-propanediol and 1, 6-hexanediol.
The plasticizer is dipropylene glycol dibenzoate or diethylene glycol dibenzoate.
The ultraviolet absorbent and light stabilizer are one or more of acetanilide, benzophenones, benzotriazoles and hindered amine.
The antioxidant is one or more of hindered phenol, hindered amine and phosphite antioxidant.
The lubricant is one or more of stearic acid, hydroxyl-terminated organic modified silicone oil and montan wax.
Catalyst stannous octoate or bismuth neodecanoate catalyst. When the catalyst is used, the catalyst is firstly diluted by polypropylene oxide dihydric alcohol (with the molecular weight of 1000), and the mass ratio of the catalyst to the polypropylene oxide dihydric alcohol is (1-4): 50.
The preparation method of the TPU master batch comprises the following steps:
adding oligomeric diol, an ultraviolet absorber, a light stabilizer, a lubricant and an antioxidant into a reaction kettle A, and controlling the material temperature at 95-120 ℃; adding diisocyanate into a reaction kettle B, and controlling the material temperature at 95-120 ℃; adding the chain extender into a reaction kettle C, and controlling the material temperature to be 95-120 ℃; then, materials in A, B, C three reaction kettles are proportionally injected into a small screw for prepolymerization, simultaneously, a catalyst is added into a pouring gate of a first area of a small screw extruder through a metering pump, a lubricant is added into a pouring gate of a second area of a large screw extruder through the metering pump, and the plasticizer is added into an exhaust port through the metering pump; and (3) extruding the materials through a double-screw extruder, and performing underwater granulation to obtain the TPU master batch.
The prepared TPU master batch has the particle size of 3-6 mm and the Shore hardness of 85A-98A.
The preparation method of the high-performance TPU film for the glass interlayer comprises the following steps:
putting the TPU master batch, the polycarbonate, the modified carbon nanofibers, the nano cobalt oxide and the antioxidant into a high-speed mixing roll, fully mixing, adding a double-screw extruder for extrusion granulation, carrying out vacuum drying, carrying out tape casting on the roll surface of a tape casting roll through a feed inlet of a tape casting machine, carrying out moving cooling on the film along with the tape casting roll and traction equipment, and further forming the film and shaping to obtain the high-performance TPU film for the glass interlayer.
The extrusion pressure of the double-screw extruder is 10-12MPa, and the rotating speed is 80-100 r/min.
The vacuum drying temperature is 80-100 deg.C, and the drying time is 2-6 h.
The TPU film material prepared by the invention is never yellowed, has strong flexibility and high transparency, has excellent impact resistance, penetration resistance and ultraviolet ray barrier property, has obvious absorption and isolation effects on blue light, can be widely applied to the fields of automobiles, electronic screens, bulletproof glass, buildings, spaceflight, railways and the like, can also be used as a decorative film of a glass interlayer, is stable and efficient in the production process, can promote the application of the TPU material in the high-end field, and has wide market prospect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a double-stage screw production process, can enhance the mixing effect of different reaction stages of materials, simulate a two-step production process, reduce crystal points and side reactions, and simultaneously can control the performance of TPU master batches by adjusting the molar ratio of NCO/OH, and the operation process is simple and easy;
(2) the modified carbon nanofiber is introduced to effectively improve the impact strength, mechanical property and antistatic property of the TPU film, the nanometer cobalt oxide improves the isolation effect of the film on short-wave blue light, and the ultraviolet isolation effect of the film is effectively improved by matching with an ultraviolet absorbent and a light stabilizer;
(3) the TPU composite material prepared by the invention has the advantages of high and stable production process, excellent thermodynamic property of the material, higher light transmittance of 90 percent, remarkable antistatic effect and surface resistance which can be reduced to 10 percent9Omega, strong ultraviolet barrier property, good low-temperature toughness and excellent rebound resilience.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
The raw materials referred to in the examples are as follows:
antioxidant 1010, basf corporation;
antioxidant 126, obtained from basf corporation;
UV resistant agent UBS available from Utility and Industrial Co;
light stabilizer 866, available from basf corporation;
lubricant: stearamide EBS, longsha, usa; montan wax, Craine corporation was used.
Example 1
A high-performance TPU film for a glass interlayer is prepared from the following raw materials in percentage by mass:
the TPU master batch is prepared from the following raw materials in percentage by mass and 0.02% of catalyst T-9 in addition:
the reaction hardness was 43% and the r-value (NCO/OH molar ratio) was 0.995.
The preparation method comprises the following steps:
(1) adding oligomeric diol, an ultraviolet absorber, a light stabilizer and an antioxidant into a reaction kettle A, and controlling the material temperature at 100 ℃; adding diisocyanate into a reaction kettle B, and controlling the material temperature at 100 ℃; adding a chain extender into the reaction kettle C, and controlling the material temperature at 100 ℃; then, materials in A, B, C three reaction kettles are proportionally injected into a small screw for prepolymerization, simultaneously, a catalyst is added into a pouring gate of a first area of a small screw extruder through a metering pump, a lubricant is added into a pouring gate of a second area of a large screw extruder through the metering pump, and the plasticizer is added into an exhaust port through the metering pump; the materials are extruded by a double-screw extruder in a reaction way, and then are granulated under water, and the extruded particles are dried for 8 hours under vacuum at 90 ℃ to obtain TPU master batch;
(2) putting the TPU master batch, the polycarbonate, the modified carbon nanofibers, the nano cobalt oxide and the antioxidant into a high-speed mixing roll, fully mixing, adding a double-screw extruder for extrusion granulation, wherein the extrusion pressure is 10MPa, the rotating speed is 80r/min, carrying out vacuum drying on the extruded particles at 80 ℃ for 2 hours, carrying out tape casting on the extruded particles to the roll surface of a tape casting roll through a feed inlet of a tape casting machine, and carrying out moving cooling on the film along with the tape casting roll and traction equipment to form a film and shape the film so as to obtain the high-performance TPU film for the glass interlayer.
Example 2
A high-performance TPU film for a glass interlayer is prepared from the following raw materials in percentage by mass:
the TPU master batch is prepared from the following raw materials in percentage by mass and 0.02% of catalyst T-9 in addition:
the reaction hardness was 43% and the r-value (NCO/OH molar ratio) was 0.995.
The preparation method is the same as that of example 1.
Example 3
A high-performance TPU film for a glass interlayer is prepared from the following raw materials in percentage by mass:
the TPU master batch is prepared from the following raw materials in percentage by mass and 0.02% of catalyst T-9 in addition:
the reaction hardness was 43% and the r-value (NCO/OH molar ratio) was 0.995.
The preparation method is the same as that of example 1.
Example 4
A high-performance TPU film for a glass interlayer is prepared from the following raw materials in percentage by mass:
the TPU master batch is prepared from the following raw materials in percentage by mass and 0.02% of catalyst T-9 in addition:
the reaction hardness was 43% and the r-value (NCO/OH molar ratio) was 0.995.
The preparation method is the same as that of example 1.
Comparative example 1
The difference between the comparative example and the example 1 is that the modified nanometer cobalt oxide is not added in the raw material formula of the TPU film, and the raw material percentage is as follows:
comparative example 2
The difference between the comparative example and the example 2 is that the modified carbon nanofibers are not added in the raw material formula of the TPU film, and the raw material percentage is as follows:
comparative example 3
The difference between the comparative example and the example 3 is that the modified nano carbon fiber and the modified nano cobalt oxide are not added in the raw material formula of the TPU film, and the raw material percentage is as follows:
85 percent of TPU master batch
14.9% of polycarbonate
1260.1 percent of antioxidant.
Comparative example 4
The comparative example is the same as the raw material formula of example 1, and is different only in that the preparation method of the TPU master batch is different, the comparative example adopts a one-step extrusion process to prepare the TPU master batch, and the preparation method of the TPU master batch is as follows:
adding oligomeric diol, an ultraviolet absorber, a light stabilizer, a lubricant, an antioxidant and a plasticizer into a reaction kettle A, and controlling the material temperature at 100 ℃; adding diisocyanate into a reaction kettle B, and controlling the material temperature at 100 ℃; adding a chain extender into the reaction kettle C, and controlling the material temperature at 100 ℃; mixing the raw material components in the reaction kettle A, the reaction kettle B and the reaction kettle C through a high-speed rotating mixing head, injecting the mixture into a double-screw extruder, simultaneously adding a catalyst into a feeding port of the double-screw extruder through a micro injection pump, uniformly reacting and conveying the mixed material in a double-screw cylinder, and granulating through water after plasticizing to obtain the TPU master batch.
Comparative example 5
The comparative example is different from example 1 only in that the oligomeric diol in the formulation of the TPU master batch raw material is replaced by PEG-2000, and the number average molecular weight is 2000.
Comparative example 6
The comparative example is different from example 1 only in that the TPU master batch is replaced by PVB master batch with equal mass percentage.
The films prepared in the examples and comparative examples were subjected to performance tests as follows:
(1) hardness: ASTM D2240;
(2) tensile strength: ASTM D638;
(3) 5% weight loss on heating: a thermal weightlessness instrument TG is arranged in a nitrogen atmosphere, the heating rate is 5 ℃/min, and the heating interval is 25-460 ℃;
(4) glass transition temperature: differential Scanning Calorimetry (DSC) in nitrogen atmosphere at-70-230 deg.C; the heating rate is 10 ℃/min;
(5) surface resistance: a resistance meter;
(6) light transmittance: and according to ASTM D1003, 380nm is selected as a representative ultraviolet light wave band, 450 is selected as a representative blue light wave band, and the transmittance is detected.
The test results are shown in table 1.
TABLE 1 film Performance index test results for each of the examples and comparative examples
As can be seen from Table 1, the high performance TPU thin film for glass interlayer of the invention can significantly improve the thermodynamic property, antistatic property, high light transmittance and ultraviolet blocking property. Compared with the example 1, the TPU film does not contain the modified nano cobalt oxide, the 380nm ultraviolet transmittance and the 450nm blue light transmittance of the TPU film are increased, and the ultraviolet and blue light prevention functions are weakened. Compared with the example 2, the TPU film does not contain the modified carbon nanofibers, the 380nm ultraviolet transmittance and the 450nm blue transmittance of the TPU film are increased, the ultraviolet and blue light prevention functions are weakened, the surface resistance is increased, and the antistatic capability is weakened. Compared with the example 3, the TPU film does not contain the modified nano cobalt oxide and the modified nano carbon fiber, the 380nm ultraviolet transmittance, the 450nm blue light transmittance and the surface resistance of the TPU film are obviously increased, the ultraviolet and blue light prevention functions are weakened, and the antistatic capability is also weakened. Compared with the embodiment 1, the preparation process of the TPU master batch is changed into the one-step extrusion process, and compared with the embodiment 1, the stability deviation and the side reaction of the product are more in the one-step process, so that the turbidity and the mechanical property of the product are influenced, and the crystal point control is difficult to meet the requirement. Compared with the embodiment 1, the TPU master batch adopts PEG-2000, the mechanical strength of the TPU film is obviously reduced, and the pure polyether diol is difficult to meet the requirement, so the polycaprolactone diol is adopted. Compared with the embodiment 1, the TPU master batch is replaced by the PVB master batch with equal mass percentage, and due to the structural difference, the tensile strength, the low-temperature flexibility and the high-temperature resistance of the PVB film are obviously inferior to those of the TPU film.
Claims (10)
1. A high-performance TPU film for a glass interlayer is characterized by being prepared from the following raw materials in percentage by mass:
2. the high performance TPU film for glass interlayers of claim 1 wherein: the TPU master batch is prepared from the following raw materials in percentage by mass and a catalyst:
the dosage of the catalyst is 0.005-0.03% of the total mass of the raw materials.
3. The high performance TPU film for glass interlayers of claim 1 wherein: the number average molecular weight of the polycarbonate is 6000-9000; the antioxidant is one or more of hindered phenol, hindered amine and phosphite antioxidant.
4. The high performance TPU film for glass interlayers of claim 1 wherein: the modified carbon nanofiber is prepared by oxidizing carbon nanofiber with concentrated acid and performing silanization modification with a silane coupling agent.
5. The high performance TPU film for glass interlayers of claim 1 wherein: the modified nano cobalt oxide is prepared by performing silanization modification on nano cobalt oxide by a silane coupling agent, and the particle size of the modified nano cobalt oxide is 300-400 nm.
6. The high performance TPU film for glass interlayers of claim 2 wherein: the oligomeric diol is one or two of polyoxypropylene diol, polycaprolactone diol and polybutylene adipate diol, and has the number average molecular weight of 800-.
7. The high performance TPU film for glass interlayers of claim 2 wherein: the diisocyanate is HMDI or HDI.
8. The high performance TPU film for glass interlayers of claim 2 wherein: the chain extender is one or more of 1, 4-butanediol, 1, 2-propanediol, 1, 3-propanediol and 1, 6-hexanediol;
the plasticizer is dipropylene glycol dibenzoate or diethylene glycol dibenzoate;
the ultraviolet absorbent and the light stabilizer are one or more of acetanilide, benzophenones, benzotriazoles and hindered amine;
the antioxidant is one or more of hindered phenol, hindered amine and phosphite ester antioxidant;
the lubricant is one or more of stearic acid amide, hydroxyl-terminated organic modified silicone oil and montan wax;
catalyst stannous octoate or bismuth neodecanoate catalyst.
9. A method of making a high performance TPU film for glass interlayers as described in any of claims 1 through 8 comprising the steps of:
(1) preparing TPU master batch: adding oligomeric diol, an ultraviolet absorber, a light stabilizer, a lubricant and an antioxidant into a reaction kettle A, and controlling the material temperature at 95-120 ℃; adding diisocyanate into a reaction kettle B, and controlling the material temperature at 95-120 ℃; adding the chain extender into a reaction kettle C, and controlling the material temperature to be 95-120 ℃; then, materials in A, B, C three reaction kettles are proportionally injected into a small screw for prepolymerization, simultaneously, a catalyst is added into a pouring gate of a first area of a small screw extruder through a metering pump, a lubricant is added into a pouring gate of a second area of a large screw extruder through the metering pump, and the plasticizer is added into an exhaust port through the metering pump; the materials are extruded by a double-screw extruder in a reaction way and then are granulated underwater to obtain TPU master batches;
(2) preparing a TPU film: putting the TPU master batch, the polycarbonate, the modified carbon nanofibers, the nano cobalt oxide and the antioxidant into a high-speed mixing roll, fully mixing, adding a double-screw extruder for extrusion granulation, carrying out vacuum drying, carrying out tape casting on the roll surface of a tape casting roll through a feed inlet of a tape casting machine, carrying out moving cooling on the film along with the tape casting roll and traction equipment, and further forming the film and shaping to obtain the high-performance TPU film for the glass interlayer.
10. The method of making a high performance TPU film for glass interlayers of claim 9 wherein: in the step (2), the extrusion pressure of the double-screw extruder is 10-12MPa, and the rotating speed is 80-100 r/min; the vacuum drying temperature is 80-100 deg.C, and the drying time is 2-6 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393829A (en) * | 2020-04-21 | 2020-07-10 | 东莞市雄林新材料科技股份有限公司 | TPU film for express packaging and preparation method thereof |
| CN112143016A (en) * | 2020-09-07 | 2020-12-29 | 浙江佳阳塑胶新材料有限公司 | Heat-insulating TUP film for mobile phone glass screen and preparation method thereof |
| CN114380977A (en) * | 2022-01-11 | 2022-04-22 | 广东康诚新材料科技股份有限公司 | TPU (thermoplastic polyurethane) shoe material and preparation method thereof |
-
2019
- 2019-08-30 CN CN201910813103.2A patent/CN110591337A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393829A (en) * | 2020-04-21 | 2020-07-10 | 东莞市雄林新材料科技股份有限公司 | TPU film for express packaging and preparation method thereof |
| CN112143016A (en) * | 2020-09-07 | 2020-12-29 | 浙江佳阳塑胶新材料有限公司 | Heat-insulating TUP film for mobile phone glass screen and preparation method thereof |
| CN114380977A (en) * | 2022-01-11 | 2022-04-22 | 广东康诚新材料科技股份有限公司 | TPU (thermoplastic polyurethane) shoe material and preparation method thereof |
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