CN110894278B - High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof - Google Patents
High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof Download PDFInfo
- Publication number
- CN110894278B CN110894278B CN201911165506.7A CN201911165506A CN110894278B CN 110894278 B CN110894278 B CN 110894278B CN 201911165506 A CN201911165506 A CN 201911165506A CN 110894278 B CN110894278 B CN 110894278B
- Authority
- CN
- China
- Prior art keywords
- parts
- polyurethane elastomer
- thermoplastic polyurethane
- weight
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- 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
- 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
- C08G18/44—Polycarbonates
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a high-transparency thermoplastic polyurethane elastomer for film blowing and a preparation method thereof, wherein the high-transparency thermoplastic polyurethane elastomer comprises the following components in parts by weight: 50-60 parts of diisocyanate; 100-150 parts by weight of polyester polyol; 40-50 parts by weight of polycarbonate; 10-15 parts of nano silicon dioxide; 5-10 parts of nano-cellulose; 5-10 parts of a chain extender; 5-7 parts by weight of a silane coupling agent; 1-5 parts of catalyst. The thermoplastic polyurethane elastomer provided by the invention has excellent transparency, proper melt index and excellent mechanical property, wherein the transparency can reach more than 90%, and the melt index is between 9 and 13g/10 min.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, relates to a thermoplastic polyurethane elastomer for film blowing and a preparation method thereof, and particularly relates to a high-transparency thermoplastic polyurethane elastomer for film blowing and a preparation method thereof.
Background
Polyurethane is a high molecular synthetic material with excellent performance, not only has the elasticity of rubber, but also has the hardness of plastics, and also has good mechanical property, wear resistance and rebound resilience, and the advantages of the polyurethane can be utilized to manufacture the wheels of the roller skates. Although the high-resilience wheel material of the polytetrahydrofuran system has good elasticity and wear resistance, the production cost is high, and the popularization of the polytetrahydrofuran system is inconvenient. The common polyether polyurethane elastomer with low price has impact resilience of below 50 percent and poor wear resistance, the comfort level of the pulley made of the polyether polyurethane elastomer is reduced when the pulley slides, the service life is short, and meanwhile, the light transmittance of the common polyurethane elastomer is below 60 percent, and the appearance is not attractive.
Blown film (Blow Membrane) is a plastic processing method, which refers to a plastic processing technology that plastic particles are heated to melt and then blown into a film, and generally, a polymer is extruded into a tubular film blank, the tubular film is blown to a required thickness by high-pressure air in a better melt flowing state, and the tubular film is formed into the film after cooling and shaping. The quality of the film material blown by the processing technology is related to the machine for blowing the film and plastic particles. The production equipment is simple, the investment is low, and the product takes effect quickly; the mechanical property of the film is high; no rim charge and less waste; the film product is cylindrical, and the bag making process is simple; can produce large-width films.
CN1284092A discloses an improved water blown polyurethane sole system comprising a molded article of microcellular polyurethane foam which is the reaction product of a and B in the presence of C, wherein a is a stable liquid MDI based prepolymer having an isocyanate content of 5-30% and containing allophanate modified MDI, B is an isocyanate reactive composition and C is a blowing agent, the amounts of components a and B being such that the isocyanate index is from about 90 to 110. CN1340069A discloses a microcellular water blown rigid polyurethane foam, a process for producing microcellular rigid polyurethane and/or polyisocyanate foams by reacting a polyisocyanate having an NCO content of 20 to 48% by weight, a polyol component in the form of an emulsion having on average at least two groups reactive with isocyanate and containing at least one at least difunctional polyol, water, a catalyst and optionally auxiliary and additive substances. Although both patents ultimately lead to polyurethanes which can be used for blow molding, the resulting polyurethanes are complicated to prepare by processes which are less transparent.
Therefore, it is necessary to develop a polyurethane elastomer with high transparency for blown film to meet the application requirements.
Disclosure of Invention
The invention aims to provide a high-transparency thermoplastic polyurethane elastomer for film blowing and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-transparency thermoplastic polyurethane elastomer for film blowing, which comprises the following components in parts by weight:
the thermoplastic polyurethane elastomer provided by the invention comprises polycarbonate and nanocellulose, and the addition of a proper amount of polycarbonate and nanocellulose can enable the finally obtained polyurethane elastomer to have higher transparency, meanwhile, the polycarbonate has more excellent toughness and excellent processability, and the nanocellulose can enhance the mechanical property of a base material, so that the addition of the polycarbonate and the nanocellulose in the polyurethane elastomer can enable the polyurethane elastomer to have higher transparency and more excellent mechanical property.
In addition, the polyurethane elastomer provided by the invention also comprises nano silica and a silane coupling agent, the compatibility of the nano silica can be increased by using the silane coupling agent, and the melt index of the polyurethane elastomer can be adjusted by adding a proper amount of the nano silica.
The addition amounts of the polycarbonate, nanocellulose, nanosilica and silane coupling agent in the present invention are required to be within the range defined in the present invention. The addition of specific amounts of nanosilica, nanocellulose, polycarbonate, etc. allows the melt index of the finally obtained polyurethane elastomer to be suitable, facilitating processing by blow molding processes.
The high transparency of the invention means that the transparency is more than 90%.
In the present invention, the diisocyanate is 50 to 60 parts by weight, for example, 52 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 58 parts by weight, 59 parts by weight, and the like.
In the present invention, the polyester polyol is 100-150 parts by weight, for example, 105 parts by weight, 110 parts by weight, 115 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, and the like.
In the present invention, the polycarbonate is 40 to 50 parts by weight, for example, 42 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 48 parts by weight, 49 parts by weight, and the like.
The polycarbonate of the present invention refers to a polycarbonate obtained by transesterification and polycondensation of bisphenol A and diphenyl carbonate.
In the present invention, the nano silica is 10 to 15 parts by weight, for example, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, and the like.
In the present invention, the nanocellulose is 5 to 10 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, and the like.
In the present invention, the chain extender is 5 to 10 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, and the like.
In the present invention, the silane coupling agent is 5 to 7 parts by weight, for example, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, and the like.
In the present invention, the catalyst is 1 to 5 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, and the like.
In the present invention, the diisocyanate is selected from the group consisting of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexylmethane diisocyanate in combination.
Preferably, the molar ratio of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate to dicyclohexylmethane diisocyanate is (1.5-2.5):1, e.g., 1.7:1, 1.8:1, 2:1, 2.2:1, 2.4:1, etc., and more preferably 1.5: 1.
When the invention prefers the combination of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexyl methane diisocyanate, the melt index of the finally obtained polyurethane elastomer is 10-12g/10min, so that the melt index is moderate, and the polyurethane elastomer can be well applied to a film blowing process.
In the present invention, the polyester polyol is selected from any one of polyethylene adipate, polyhexamethylene adipate, or polybutylene adipate, or a combination of at least two thereof.
Preferably, the polyester polyols have molecular weights of 1000-.
In the present invention, the molecular weight of the polycarbonate is 10000-.
Preferably, the mass ratio of the nano silica to the silane coupling agent is 2: 1.
When the mass ratio of the nano silicon dioxide to the silane coupling agent is 2:1, the silane coupling agent has a good effect of improving the compatibility of the nano silicon dioxide and the matrix resin.
Preferably, the chain extender is any one or a combination of at least two of dihydric alcohol and/or diamine, and further preferably ethylene glycol, ethylenediamine, 1, 3-propanediol or 1, 5-pentanediol.
Preferably, the silane coupling agent is isobutyltriethoxysilane and/or vinyltriethoxysilane.
Preferably, the catalyst is any one of stannous octoate, dibutyltin dioctoate or dibutyltin laurate or a combination of at least two of the stannous octoate, the dibutyltin dioctoate or the dibutyltin laurate.
In a second aspect, the present invention provides a method for producing a highly transparent thermoplastic polyurethane elastomer for blown film according to the first aspect, the method comprising the steps of:
(1) mixing polyester polyol, nano-cellulose, a chain extender and a catalyst;
(2) mixing diisocyanate, polycarbonate, nano silicon dioxide and a silane coupling agent;
(3) and (3) mixing the mixture obtained in the step (1) and the mixture obtained in the step (2), adding the mixture into a double-screw extruder, and performing extrusion molding and granulation to obtain the high-transparency thermoplastic polyurethane elastomer for film blowing.
The preparation method provided by the invention can ensure that the additive in the polyurethane elastomer is dispersed more uniformly, so that the finally obtained thermoplastic polyurethane elastomer has better performance.
The nano-cellulose is mixed with the polyester polyol, and hydroxyl groups of the nano-cellulose can form hydrogen bonds with hydroxyl groups of the polyester polyol, so that the dispersibility of the nano-cellulose can be improved, and the agglomeration of the nano-cellulose is avoided; meanwhile, the nano silicon dioxide and the silane coupling agent are mixed together to increase the dispersibility of the nano silicon dioxide, and the two mixtures are mixed, so that the nano cellulose and the nano silicon dioxide in the thermoplastic polyurethane elastomer obtained finally have better dispersibility, and the agglomeration is avoided.
Preferably, the temperature of the feeding section of the twin-screw extruder in step (3) is 190-.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing polyester polyol, nano-cellulose, a chain extender and a catalyst;
(2) mixing diisocyanate, polycarbonate, nano silicon dioxide and a silane coupling agent;
(3) mixing the mixture obtained in the step (1) and the mixture obtained in the step (2), adding the mixture into a double-screw extruder, and performing extrusion molding and granulation to obtain the high-transparency thermoplastic polyurethane elastomer for film blowing; wherein the temperature of the feeding section of the double-screw extruder is 190-.
Compared with the prior art, the invention has the following beneficial effects:
(1) the thermoplastic polyurethane elastomer provided by the invention comprises polycarbonate and nanocellulose, and the addition of a proper amount of polycarbonate and nanocellulose can enable the finally obtained polyurethane elastomer to have higher transparency, meanwhile, the polycarbonate has more excellent toughness and excellent processability, and the nanocellulose can enhance the mechanical property of a base material, so that the addition of the polycarbonate and the nanocellulose in the polyurethane elastomer can enable the polyurethane elastomer to have higher transparency and more excellent mechanical property;
(2) the addition amounts of the polycarbonate, nanocellulose, nanosilica and silane coupling agent in the present invention are required to be within the range defined in the present invention. The addition of nano silicon dioxide, nano cellulose, polycarbonate and the like with specific contents can ensure that the finally obtained polyurethane elastomer has proper melt index, thereby being beneficial to processing by a blow molding process;
(3) the thermoplastic polyurethane elastomer provided by the invention has excellent transparency, proper melt index and excellent mechanical property, wherein the transparency can reach more than 90%, and the melt index is between 9 and 13g/10 min.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A high-transparency thermoplastic polyurethane elastomer for blown film comprises the following components in parts by weight:
wherein, the diisocyanate is a composition consisting of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexylmethane diisocyanate according to the molar ratio of 1.5: 1; the polyester polyol is polybutylene adipate with the average molecular weight of 1500; the molecular weight of the polycarbonate was 15000; the average grain diameter of the nano silicon dioxide is 80 nm; the diameter of the nano-cellulose is 40-60nm, and the length-diameter ratio is 250-300; the chain extender is ethylene glycol; the silane coupling agent is isobutyl triethoxy silane; the catalyst is stannous octoate.
The preparation method comprises the following steps:
(1) mixing polyester polyol, nano-cellulose, a chain extender and a catalyst;
(2) mixing diisocyanate, polycarbonate, nano silicon dioxide and a silane coupling agent;
(3) mixing the mixture obtained in the step (1) and the mixture obtained in the step (2), adding the mixture into a double-screw extruder, and performing extrusion molding and granulation to obtain a high-transparency thermoplastic polyurethane elastomer for film blowing; wherein the temperature of the feeding section of the double-screw extruder is 195 ℃, the temperature of the mixing section is 205 ℃, the temperature of the extrusion section is 215 ℃, and the temperature of the machine head is 215 ℃.
Examples 2 to 4
The only difference from example 1 is that the molar ratio of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate to dicyclohexylmethane diisocyanate was 2.5:1 (example 2), 3:1 (example 3), 1:1 (example 4).
Examples 5 to 6
The only difference from example 1 is that the diisocyanate is 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate (example 5) or dicyclohexylmethane diisocyanate (example 6).
Examples 7 to 8
The only difference from example 1 is that the amount of the silane coupling agent added was 5 parts by weight (example 7) and 7 parts by weight (example 8).
Example 9
A high-transparency thermoplastic polyurethane elastomer for blown film comprises the following components in parts by weight:
wherein, the diisocyanate is a composition consisting of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexylmethane diisocyanate according to the molar ratio of 1.5: 1; the polyester polyol is polyethylene glycol adipate with the average molecular weight of 1000; the molecular weight of the polycarbonate is 10000; the average grain diameter of the nano silicon dioxide is 80 nm; the diameter of the nano-cellulose is 40-60nm, and the length-diameter ratio is 250-300; the chain extender is ethylene glycol; the silane coupling agent is isobutyl triethoxy silane; the catalyst is dibutyltin dioctoate.
The preparation method comprises the following steps:
(1) mixing polyester polyol, nano-cellulose, a chain extender and a catalyst;
(2) mixing diisocyanate, polycarbonate, nano silicon dioxide and a silane coupling agent;
(3) mixing the mixture obtained in the step (1) and the mixture obtained in the step (2), adding the mixture into a double-screw extruder, and performing extrusion molding and granulation to obtain a high-transparency thermoplastic polyurethane elastomer for film blowing; wherein the temperature of the feeding section of the double-screw extruder is 190 ℃, the temperature of the mixing section is 200 ℃, the temperature of the extrusion section is 210 ℃, and the temperature of the machine head is 210 ℃.
Example 10
A high-transparency thermoplastic polyurethane elastomer for blown film comprises the following components in parts by weight:
wherein, the diisocyanate is a composition consisting of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexylmethane diisocyanate according to the molar ratio of 1.5: 1; the polyester polyol is polybutylene adipate with the average molecular weight of 2000; the molecular weight of the polycarbonate is 20000; the average grain diameter of the nano silicon dioxide is 80 nm; the diameter of the nano-cellulose is 40-60nm, and the length-diameter ratio is 250-300; the chain extender is 1, 5-pentanediol; the silane coupling agent is vinyl triethoxysilane; the catalyst is dibutyl tin laurate.
The preparation method comprises the following steps:
(1) mixing polyester polyol, nano-cellulose, a chain extender and a catalyst;
(2) mixing diisocyanate, polycarbonate, nano silicon dioxide and a silane coupling agent;
(3) mixing the mixture obtained in the step (1) and the mixture obtained in the step (2), adding the mixture into a double-screw extruder, and performing extrusion molding and granulation to obtain a high-transparency thermoplastic polyurethane elastomer for film blowing; wherein the temperature of the feeding section of the double-screw extruder is 200 ℃, the temperature of the mixing section is 210 ℃, the temperature of the extrusion section is 220 ℃, and the temperature of the machine head is 220 ℃.
Comparative examples 1 to 2
The difference from example 1 is that the polycarbonate was added in an amount of 35 parts by weight (comparative example 1) and 55 parts by weight (comparative example 2).
Comparative examples 3 to 4
The difference from example 1 is that the amount of nanocellulose added was 1 part by weight (comparative example 3) and 15 parts by weight (comparative example 4).
Comparative examples 5 to 6
The difference from example 1 is that the amount of the nano silica added was 1 part by weight (comparative example 5) and 15 parts by weight (comparative example 6).
Comparative examples 7 to 8
The difference from example 1 was that the silane coupling agent was added in an amount of 1 part by weight (comparative example 7) and 10 parts by weight (comparative example 8).
Performance testing
The samples provided in examples 1-10 and comparative examples 1-8 were tested for performance by the following method:
(1) melt index: melt index was measured by ASTM D1238 at 220 ℃ with a 10kg weight;
(2) light transmittance: testing by using a light transmittance tester;
(3) mechanical properties: the test was performed according to GB/T528-2009 test standard.
The test results are shown in table 1:
TABLE 1
The embodiment and the performance test show that the thermoplastic polyurethane elastomer provided by the invention has high transparency, moderate melt index and excellent mechanical property, wherein the transparency can reach more than 90%, the melt index is between 9 and 13g/10min, the tensile strength is more than 65MPa, and the elongation at break is more than 100%.
As can be seen from the comparison between example 1 and examples 2 to 6, when the combination of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexylmethane diisocyanate is preferred in the present invention, the melt index of the finally obtained polyurethane elastomer of the present invention is 10 to 12g/10min, so that the melt index is moderate, and the polyurethane elastomer can be well applied to the film blowing process; if the melt index is too large, the fluidity is too good, and if the melt index is too small, the fluidity is too poor, and both of them affect the film blowing process. As is clear from the comparison between example 1 and comparative examples 1 to 8, the polycarbonate, nanocellulose, nanosilica and silane coupling agent of the present invention should be added in an amount within the range defined by the present invention, and too much or too little of them does not achieve the object of the present invention.
The applicant states that the present invention is illustrated by the above examples of the highly transparent thermoplastic polyurethane elastomer for blown film and the method for preparing the same according to the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must be carried out depending on the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (11)
1. A high-transparency thermoplastic polyurethane elastomer for blown film is characterized by comprising the following components in parts by weight:
50-60 parts of diisocyanate;
100-150 parts by weight of polyester polyol;
40-48 parts of polycarbonate;
10-14 parts of nano silicon dioxide;
5-10 parts of nano-cellulose;
5-10 parts of a chain extender;
5-7 parts by weight of a silane coupling agent;
1-5 parts of a catalyst;
the diisocyanate is selected from the group consisting of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexylmethane diisocyanate;
the molar ratio of the 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate to the dicyclohexylmethane diisocyanate is (1.5-2.5) to 1;
the mass ratio of the nano silicon dioxide to the silane coupling agent is 2: 1.
2. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 1, characterized in that the molar ratio of 3,3 '-dimethyl-4, 4' -biphenyl diisocyanate and dicyclohexylmethane diisocyanate is 1.5: 1.
3. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 1, wherein the polyester polyol is selected from any one of polyethylene adipate, polyhexamethylene adipate, or polybutylene adipate, or a combination of at least two thereof.
4. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 1, wherein the molecular weight of the polyester polyol is 1000-2000.
5. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 1, wherein the molecular weight of the polycarbonate is 10000-.
6. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 1, wherein the chain extender is a diol and/or a diamine.
7. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 6, wherein the chain extender is any one of ethylene glycol, ethylene diamine, 1, 3-propanediol or 1, 5-pentanediol or a combination of at least two thereof.
8. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 1, wherein said silane coupling agent is isobutyltriethoxysilane and/or vinyltriethoxysilane.
9. The highly transparent thermoplastic polyurethane elastomer for blown film according to claim 1, wherein the catalyst is any one of stannous octoate, dibutyltin dioctoate or dibutyltin laurate or a combination of at least two thereof.
10. The production method of a highly transparent thermoplastic polyurethane elastomer for blown film according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) mixing polyester polyol, nano-cellulose, a chain extender and a catalyst;
(2) mixing diisocyanate, polycarbonate, nano silicon dioxide and a silane coupling agent;
(3) and (3) mixing the mixture obtained in the step (1) and the mixture obtained in the step (2), adding the mixture into a double-screw extruder, and performing extrusion molding and granulation to obtain the high-transparency thermoplastic polyurethane elastomer for film blowing.
11. The method as claimed in claim 10, wherein the temperature of the feeding section of the twin-screw extruder in step (3) is 190-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911165506.7A CN110894278B (en) | 2019-11-25 | 2019-11-25 | High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911165506.7A CN110894278B (en) | 2019-11-25 | 2019-11-25 | High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110894278A CN110894278A (en) | 2020-03-20 |
| CN110894278B true CN110894278B (en) | 2021-09-28 |
Family
ID=69786799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911165506.7A Active CN110894278B (en) | 2019-11-25 | 2019-11-25 | High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110894278B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126218A (en) * | 2020-08-28 | 2020-12-25 | 东莞市吉鑫高分子科技有限公司 | Antibacterial thermoplastic polyurethane elastomer for blow molding and preparation method thereof |
| CN112226066B (en) * | 2020-09-22 | 2021-09-24 | 东莞市雄林新材料科技股份有限公司 | TPU (thermoplastic polyurethane) anti-slip gasket and preparation method thereof |
| CN112239595B (en) * | 2020-09-22 | 2021-12-28 | 东莞市雄林新材料科技股份有限公司 | High-transparency TPU (thermoplastic polyurethane) film for electronic products and preparation method thereof |
| CN112480361B (en) * | 2020-12-01 | 2022-03-08 | 上海恒安聚氨酯股份有限公司 | Preparation method of moisture-permeable thermoplastic polyurethane film |
| CN115403919A (en) * | 2022-09-01 | 2022-11-29 | 上海雄林新材料科技有限公司 | Washable TPU (thermoplastic polyurethane) home textile membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0543646A (en) * | 1991-08-14 | 1993-02-23 | Kuraray Co Ltd | Production of thermoplastic polyurethane |
| CN104193957A (en) * | 2014-09-17 | 2014-12-10 | 朱忠良 | Transparent TPU (thermoplastic Polyurethane) film and preparation method thereof |
| CN107652664A (en) * | 2017-09-28 | 2018-02-02 | 东莞市雄林新材料科技股份有限公司 | A kind of photosensitive colour-changing TPU film for adhering film to glass and preparation method thereof |
| CN108503783A (en) * | 2018-04-11 | 2018-09-07 | 苏州大学 | Thermoplastic polyurethane elastomer and preparation method thereof |
-
2019
- 2019-11-25 CN CN201911165506.7A patent/CN110894278B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0543646A (en) * | 1991-08-14 | 1993-02-23 | Kuraray Co Ltd | Production of thermoplastic polyurethane |
| CN104193957A (en) * | 2014-09-17 | 2014-12-10 | 朱忠良 | Transparent TPU (thermoplastic Polyurethane) film and preparation method thereof |
| CN107652664A (en) * | 2017-09-28 | 2018-02-02 | 东莞市雄林新材料科技股份有限公司 | A kind of photosensitive colour-changing TPU film for adhering film to glass and preparation method thereof |
| CN108503783A (en) * | 2018-04-11 | 2018-09-07 | 苏州大学 | Thermoplastic polyurethane elastomer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110894278A (en) | 2020-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110894278B (en) | High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof | |
| JP7361415B2 (en) | Yellowing-resistant thermoplastic polyurethane foam material and method for producing the same | |
| CN111548472A (en) | High-weather-resistance ultra-transparent thermoplastic polyurethane elastomer and preparation method thereof | |
| CN112239595B (en) | High-transparency TPU (thermoplastic polyurethane) film for electronic products and preparation method thereof | |
| CN110283438B (en) | Base resin for blow molding degradable film and blow molding degradable film | |
| CN110760168B (en) | Thermoplastic polyester elastomer foaming particles and preparation method thereof | |
| CN112358844B (en) | Never-yellowing TPU (thermoplastic polyurethane) film glue for coating and preparation method and application thereof | |
| CN110885550A (en) | Organic silicon modified thermoplastic polyurethane elastomer and preparation method thereof | |
| CN110835464B (en) | Never-yellowing TPU film and preparation method thereof | |
| CN113980230A (en) | Moisture-resistant thermoplastic polyurethane elastomer material and preparation method thereof | |
| CA3131813A1 (en) | Soft particle foam consisting of thermoplastic polyurethane | |
| CN110563917B (en) | Online modified PPC resin and preparation process thereof | |
| CN111995728A (en) | Non-polar modified TPU (thermoplastic polyurethane) for shoe material and preparation method thereof | |
| KR20170069545A (en) | Transparent composite composition, method for preparing the composites using the same | |
| CN111499826B (en) | Thermoplastic polyurethane elastomer and preparation method thereof | |
| WO1981003027A1 (en) | Blends of thermoplastic polyurethane elastomers and acetal resins | |
| TW202330749A (en) | Damping pad with low compression set | |
| EP3222645B1 (en) | Thermoplastic polyurethane resin composition having enhanced texture and durability and production method thereof | |
| CN114031928B (en) | High hardness thermoplastic polyurethane elastomer composition suitable for extrusion and preparation method thereof | |
| CN110903634A (en) | Low-shrinkage rapid-forming TPU (thermoplastic polyurethane) for rubber wheel injection molding and preparation method thereof | |
| JP3447101B2 (en) | Method for producing thermoplastic polyurethane elastomer molded article | |
| CN109824981B (en) | High-toughness polypropylene plastic and preparation method and application thereof | |
| CN116217882A (en) | Invisible car cover high-strength low-haze TPU and preparation method thereof | |
| CN113831502B (en) | Preparation method of high-hardness transparent TPU | |
| CN111040424B (en) | Transparency-controllable TPU (thermoplastic polyurethane) film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |