CN116874726A - TPU material for rubber coating acrylic flat plate sheath and preparation method thereof - Google Patents
TPU material for rubber coating acrylic flat plate sheath and preparation method thereof Download PDFInfo
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- CN116874726A CN116874726A CN202310910192.9A CN202310910192A CN116874726A CN 116874726 A CN116874726 A CN 116874726A CN 202310910192 A CN202310910192 A CN 202310910192A CN 116874726 A CN116874726 A CN 116874726A
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- tpu
- acrylic flat
- flat plate
- encapsulated
- diisocyanate
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- 239000000463 material Substances 0.000 title claims abstract description 91
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000010073 coating (rubber) Methods 0.000 title description 7
- 239000002245 particle Substances 0.000 claims abstract description 34
- 229920000728 polyester Polymers 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 238000005520 cutting process Methods 0.000 claims abstract description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- -1 polyethylene adipate Polymers 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000012170 montan wax Substances 0.000 claims description 4
- 239000001993 wax Substances 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- PMDHMYFSRFZGIO-UHFFFAOYSA-N 1,4,7-trioxacyclotridecane-8,13-dione Chemical compound O=C1CCCCC(=O)OCCOCCO1 PMDHMYFSRFZGIO-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940106012 diethylene glycol adipate Drugs 0.000 claims description 2
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- LADVLFVCTCHOAI-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.CC1=CC=CC=C1 LADVLFVCTCHOAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 abstract description 68
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002313 adhesive film Substances 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 239000000806 elastomer Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract 2
- 230000003179 granulation Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 8
- 150000001718 carbodiimides Chemical class 0.000 description 7
- 238000005538 encapsulation Methods 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 3
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 3
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to a TPU material for an encapsulated acrylic flat plate sheath and a preparation method thereof. The TPU material for encapsulating the acrylic flat sheath consists of a material I and a material II, wherein the material I consists of the following raw materials: polyester diol, diisocyanate, chain extender, antioxidant, lubricant, hydrolysis inhibitor and catalyst. In the production process of the second material, the second material is a TPU product with the model T2195, and the first material with the free hydroxyl type TPU adhesive film product introduced is additionally conveyed in a double-screw temperature second area of a pouring port of the second material, so that the first material and the second material are fully fused and mutually modified in the double-screw, and the two TPU materials are subjected to re-granulation and granulation through an underwater cutting system to obtain final TPU particles, so that the second material has good molding processability and extremely high adhesive strength with an acrylic flat plate, and the effect of encapsulating the acrylic flat plate is excellent.
Description
Technical Field
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to a TPU material for an encapsulated acrylic flat plate sheath and a preparation method thereof.
Background
TPU (thermoplastic polyurethane elastomer) has a linear molecular structure, is plasticized by heating, has good wear resistance, oil resistance and chemical resistance, and has high strength and good elasticity, and is widely applied to a plurality of fields such as shoe materials, mobile phone sheaths, pipes, films, medical treatment, sports, national defense and the like. Especially in the field of mobile phone sheaths, the dosage is very large. At present, the matrix of the TPU encapsulated flat plate sheath mainly comprises a PC plate, an acrylic plate and the like. PC boards have been widely used because of their polarity similar to TPU's, which results in good encapsulation with TPU's. Compared with the former, the acrylic plate and the TPU have larger phase difference, so that the bonding strength is reduced, and the qualification rate and the service life of the whole panel sheath are directly influenced.
The acrylic plate is also called organic glass, and is good in weather resistance, acid and alkali resistance, unlikely to yellow and hydrolyze, long in service life, relatively better in light transmittance and transparency, so that the current brand high-end mobile phone sheath is more and more prone to the acrylic plate sheath, and therefore the technical means are needed to improve the bonding strength between the TPU and the acrylic plate so as to meet the encapsulation effect of the high-end brand plate sheath, improve the qualification rate of the TPU encapsulated acrylic plate sheath, prolong the service life and improve the processing efficiency.
Patent CN106117493a discloses a preparation method of a heat-resistant TPU film, which uses a component a, organic diisocyanate and small molecular diol as raw materials, wherein the component a is polyether polyol and/or polyester polyol, and the raw materials are respectively heated to melt, and in the melting process of the component a, antioxidant, carbodiimide and E wax are added, and then extruded and granulated together with the organic diisocyanate and the small molecular diol in a double screw extruder.
Patent CN104017167a discloses a preparation method of heat-resistant polyester type thermoplastic polyurethane elastomer, which comprises the following steps: adding polyester polyol and a catalyst into a reaction kettle, and dehydrating under heating and vacuum conditions to obtain a component A; and respectively heating the 1, 5-naphthalene diisocyanate and the chain extender, uniformly mixing with the component A, and then extruding the mixture through a double-screw extruder for reaction to obtain the polyester polyurethane elastomer.
In the prior art disclosed in the above patent, the production efficiency is reduced by the way of simple blending modification and reprocessing of downstream added modified materials in the industry, and the operation steps are increased.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the TPU material for the rubber coating acrylic flat plate sheath, which can effectively improve the bonding strength between TPU and acrylic plates and improve the rubber coating effect.
The invention also provides a preparation method, which reduces processing steps, improves processing efficiency and can realize industrial production.
The TPU material for the encapsulated acrylic flat plate sheath consists of a material I and a material II, wherein the material I consists of the following raw materials in percentage by mass:
the second material is a TPU product with the model of T2195;
the mixing mass ratio of the first material to the second material is 1 (9-19).
The polyester diol is one of polyethylene glycol adipate, polybutylene adipate, polyethylene glycol adipate and polyethylene glycol diethylene glycol adipate, and has a number average molecular weight of 1000-1200, preferably polybutylene adipate.
The diisocyanate is one of 4,4 '-diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene isocyanate and phenylene-1, 4-diisocyanate, preferably 4,4' -diphenylmethane diisocyanate (MDI-100).
The chain extender is one of ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol, preferably 1, 4-Butanediol (BDO).
The antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants, preferably antioxidant 1010 and antioxidant 168.
The lubricant is one of glyceryl monostearate, pentaerythritol stearate, montan wax or OP wax, preferably montan wax.
The hydrolysis resistance agent is carbodiimide.
The catalyst is one of organobismuth catalysts, organotin catalysts and titanate catalysts, and preferably an organotin catalyst T-9 (stannous octoate).
The T2195 is a common mobile phone encapsulation series commercial product of Shandong Yinuowei polyurethane stock.
The preparation method of the TPU material for the encapsulated acrylic flat sheath comprises the following steps:
(1) Mixing and heating polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A to 90-130 ℃, heating diisocyanate to 50-80 ℃ in a reaction kettle B, heating a chain extender to 55-80 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain TPU particles;
(2) Adding TPU particles into external conveying equipment, setting a certain proportion of flow, injecting in a double-screw temperature two-zone of a pouring port for producing T2195, enabling the T2195 and the TPU particles to fully react in the double-screw, granulating through an underwater cutting system, and forming new TPU particles, thus obtaining the TPU material for the encapsulated acrylic flat plate sheath.
The flow rate in the step (2) is 50-100kg/h.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the production process of the common rubber coating acrylic flat plate sheath TPU material, high hydroxyl TPU particles are introduced, the adding proportion of the first material and the second material is controlled, and under the premise of ensuring the normal processing and forming period, the hydrogen bond is increased, the hydrogen bond binding force between the rubber coating acrylic flat plate sheath TPU material and the acrylic flat plate sheath is stronger, and the rubber coating effect is improved.
(2) The method for modifying the two materials by simple banburying and blending and modifying the filler in the industry is abandoned, one TPU particle is added into a second temperature zone in the TPU double screw process in the production process under the transportation of external equipment, so that the TPU material is mutually modified and enhanced to obtain a new TPU material, the steps and procedures for continuously and downstream processing and modifying the material in the industry are reduced, the processing is in place, and the production is convenient and easy.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. All materials used in the examples are commercially available products, except as specified. The catalyst was used in a very small amount, and the following examples and comparative examples were not based on the total mass fraction.
Example 1
The TPU material for encapsulating the acrylic flat sheath comprises a material I and a material II, wherein the material I comprises the following components in percentage by mass:
polyester type dihydric alcohol: 80.13%;
MDI-100：18.3％；
BDO：1.07％；
antioxidant 1010:0.15%;
montan wax: 0.25%;
carbodiimide: 0.1%;
T-9：0.004％；
the second material is of the model T2195;
the polyester diol is polyethylene glycol adipate, the number average molecular weight is 1200, and the hydroxyl value is 93.5mgKOH/g.
The preparation method of the TPU material for the encapsulated acrylic flat sheath comprises the following steps:
(1) Mixing and heating polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A to 115 ℃, heating diisocyanate to 55 ℃ in a reaction kettle B, heating a chain extender to 55 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain TPU particles;
(2) Adding TPU particles into an external conveying device, wherein the conveying flow is 100kg/h, injecting the TPU particles into a double-screw second temperature zone for producing T2195, and the mass ratio of the T2195 to the TPU particles is 9: and 1, fully reacting and combining T2195 and external TPU particles in the production process in a double screw, and re-granulating and granulating by an underwater cutting system to form new TPU particles, thus obtaining the TPU material for the encapsulated acrylic flat plate sheath.
Example 2
The TPU material for encapsulating the acrylic flat sheath comprises a material I and a material II, wherein the material I comprises the following components in percentage by mass:
polyester type dihydric alcohol: 73.5%;
MDI-100：22.85％；
BDO：2.95％；
antioxidant 168:0.25%;
glycerol monostearate: 0.15%;
carbodiimide: 0.3%;
T-9：0.007％；
the second material is of the model T2195;
the polyester diol is polybutylene adipate, the number average molecular weight is 1100, and the hydroxyl value is 102mgKOH/g.
The preparation method of the TPU material for the encapsulated acrylic flat sheath comprises the following steps:
(1) Mixing and heating polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A to 120 ℃, heating diisocyanate to 60 ℃ in a reaction kettle B, heating a chain extender to 60 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain TPU particles;
(2) Adding TPU particles into an external conveying device, wherein the conveying flow is 50kg/h, injecting the TPU particles into a double-screw second temperature zone for producing T2195, and the mass ratio of the T2195 to the TPU particles is 19: and 1, fully reacting and combining T2195 and external TPU particles in the production process in a double screw, and re-granulating and granulating by an underwater cutting system to form new TPU particles, thus obtaining the TPU material for the encapsulated acrylic flat plate sheath.
Example 3
The TPU material for encapsulating the acrylic flat sheath comprises a material I and a material II, wherein the material I comprises the following components in percentage by mass:
polyester type dihydric alcohol: 77.3%;
MDI-100：20.92％；
BDO：1.18％；
antioxidant 1010:0.2%;
OP wax: 0.2%;
carbodiimide: 0.2%;
T-9：0.005％；
the second material is of the model T2195;
the polyester diol is polybutylene adipate, the number average molecular weight is 1000, and the hydroxyl value is 112.2mgKOH/g.
The preparation method of the TPU material for the encapsulated acrylic flat sheath comprises the following steps:
(1) Mixing and heating polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A to 105 ℃, heating diisocyanate to 65 ℃ in a reaction kettle B, heating a chain extender to 70 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain TPU particles;
(2) Adding TPU particles into an external conveying device, wherein the conveying flow is 80kg/h, injecting the TPU particles into a double-screw second temperature zone for producing T2195, and the mass ratio of the T2195 to the TPU particles is 11.5: and 1, fully reacting and combining T2195 and external TPU particles in the production process in a double screw, and re-granulating and granulating by an underwater cutting system to form new TPU particles, thus obtaining the TPU material for the encapsulated acrylic flat plate sheath.
Comparative example 1
The preparation process of T2195 comprises the following steps:
polyester type dihydric alcohol: 50.3%;
MDI-100：38.6％；
BDO：10.5％；
antioxidant 168:0.2%;
pentaerythritol stearate: 0.3%;
carbodiimide: 0.1%;
T-9：0.007％；
the polyester diol is polybutylene adipate, the number average molecular weight is 2000, and the hydroxyl value is 56.1mgKOH/g.
The preparation process is as follows: mixing polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A, heating to 115 ℃, heating diisocyanate to 75 ℃ in a reaction kettle B, heating a chain extender to 60 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain T2195 particles.
Comparative example 2
The preparation of the adhesive film TPU prepared from the material I only comprises the following materials:
polyester type dihydric alcohol: 73.5%;
MDI-100：22.85％；
BDO：2.95％；
antioxidant 168:0.25%;
glycerol monostearate: 0.15%;
carbodiimide: 0.3%;
T-9：0.007％；
the polyester diol is polybutylene adipate, the number average molecular weight is 1100, and the hydroxyl value is 102mgKOH/g.
The preparation process is as follows: mixing and heating polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A to 115 ℃, heating diisocyanate to 75 ℃ in a reaction kettle B, heating a chain extender to 60 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain TPU particles.
Comparative example 3
The TPU material is prepared by simply blending a first material and a second material:
the material I is prepared from the following components in percentage by mass:
polyester type dihydric alcohol: 73.5%;
MDI-100：22.85％；
BDO：2.95％；
antioxidant 168:0.25%;
glycerol monostearate: 0.15%;
carbodiimide: 0.3%;
T-9：0.007％；
the second material is of the model T2195;
the polyester diol is polybutylene adipate, the number average molecular weight is 1100, and the hydroxyl value is 102mgKOH/g.
The preparation process is as follows:
(1) Mixing and heating polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A to 115 ℃, heating diisocyanate to 75 ℃ in a reaction kettle B, heating a chain extender to 60 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain TPU particles of a material I.
(2) The T2195 particles of the material II and the TPU particles of the material I are mixed according to the mass ratio of 9:1, mixing uniformly, and directly adding into a screw rod of an injection molding machine for banburying and blending.
The characterization method of the encapsulation effect of the high-end brand product is a cold and hot test, namely, after the high-temperature placement for 24 hours at 80 ℃, the high-end brand product is placed for 24 hours at minus 20 ℃ and then is placed at normal temperature for 24 hours, and the bonding strength between the TPU and the acrylic flat plate is tested by a universal tensile machine to be more than or equal to 15N/mm, so that the product is qualified.
The test data for examples 1-3 and comparative examples 1-3 are as follows:
as can be seen from the detection data, the adhesive film product is not added in the comparative example 1, and the adhesive strength difference of the adhesive film product does not meet the requirement although the injection molding time is the fastest; comparative example 1 is a film product, which has the highest bonding strength, but low hardness, too long injection molding time and completely affects the processing efficiency; comparative example 3 is a simple blending of material one and material two, which results in very unstable hardness, bond strength and injection molding time, and the two materials cannot be fully and uniformly mixed, and cannot meet the processing and encapsulation requirements. According to the embodiments 1-3, after the first adhesive film product is introduced in a specific manner, the bonding strength between the TPU and the acrylic flat plate can reach more than 20N/mm, the injection molding period is obviously and basically not influenced, the second material has the function of modifying and enhancing the bonding strength, the second material has the function of enhancing the hardness and improving the processing, and the TPU is modified and enhanced by introducing the other material in the production process of one material, supports each other and enhances the encapsulation effect.
Claims (10)
1. The TPU material for the encapsulated acrylic flat plate sheath is characterized by comprising a material I and a material II, wherein the material I comprises the following raw materials in percentage by mass:
the second material is a TPU product with the model of T2195;
the mixing mass ratio of the first material to the second material is 1 (9-19).
2. The TPU material for an encapsulated acrylic flat sheet jacket of claim 1, wherein said polyester diol is one of polyethylene adipate, polybutylene adipate, polyethylene glycol diethylene glycol adipate.
3. The TPU material for an encapsulated acrylic flat sheet jacket according to claim 1, wherein said diisocyanate is one of 4,4' -diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene isocyanate, phenylene-1, 4-diisocyanate.
4. The TPU material for an encapsulated acrylic flat sheet jacket of claim 1, wherein said chain extender is one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol.
5. The TPU material for an encapsulated acrylic flat panel jacket according to claim 1, wherein the antioxidant is one or more of hindered phenolic antioxidants and phosphite antioxidants.
6. The TPU material for an encapsulated acrylic flat sheet jacket according to claim 1, wherein said lubricant is one of glyceryl monostearate, pentaerythritol stearate, montan wax or OP wax.
7. The TPU material for an encapsulated acrylic flat sheet jacket of claim 1, wherein said hydrolysis inhibitor is a carbodiimide.
8. The TPU material for an encapsulated acrylic flat sheet jacket of claim 1, wherein said catalyst is one of organobismuth, organotin, titanate catalysts.
9. A process for preparing a TPU material for encapsulating an acrylic flat sheath according to any of claims 1-8, comprising the steps of:
(1) Mixing and heating polyester dihydric alcohol, an antioxidant, a lubricant, a hydrolysis inhibitor, a catalyst and a reaction kettle A to 90-130 ℃, heating diisocyanate to 50-80 ℃ in a reaction kettle B, heating a chain extender to 55-80 ℃ in a reaction kettle C, uniformly mixing the three components according to a proportion, adding the mixture into a double-screw extruder, and granulating by an underwater cutting system to obtain TPU particles;
(2) Adding TPU particles into external conveying equipment, setting a certain proportion of flow, injecting in a double-screw temperature two-zone of a pouring port for producing T2195, enabling the T2195 and the TPU particles to fully react in the double-screw, granulating through an underwater cutting system, and forming new TPU particles, thus obtaining the TPU material for the encapsulated acrylic flat plate sheath.
10. The method of claim 9, wherein the flow rate in step (2) is 50-100kg/h.
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