CN115093550A - High-whiteness film and preparation method thereof - Google Patents
High-whiteness film and preparation method thereof Download PDFInfo
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- CN115093550A CN115093550A CN202110897002.5A CN202110897002A CN115093550A CN 115093550 A CN115093550 A CN 115093550A CN 202110897002 A CN202110897002 A CN 202110897002A CN 115093550 A CN115093550 A CN 115093550A
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- acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000006085 branching agent Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 23
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 12
- PJXWYLSAKUNJSC-UHFFFAOYSA-N 1-[bis(2-hydroxypropyl)amino]propan-2-ol;octadecanoic acid Chemical compound CC(O)CN(CC(C)O)CC(C)O.CCCCCCCCCCCCCCCCCC(O)=O PJXWYLSAKUNJSC-UHFFFAOYSA-N 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000000071 blow moulding Methods 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- RZEWIYUUNKCGKA-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanol;octadecanoic acid Chemical compound OCCNCCO.CCCCCCCCCCCCCCCCCC(O)=O RZEWIYUUNKCGKA-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkyl titanic acid Chemical compound 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims 1
- 229920006267 polyester film Polymers 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract description 2
- 230000003628 erosive effect Effects 0.000 abstract 1
- 239000001384 succinic acid Substances 0.000 description 5
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention discloses a high-whiteness film, which comprises the following preparation raw materials in parts by weight: 30-60 parts of terephthalic acid, 40-55 parts of 1, 4-butanediol, 0.02-0.1 part of branching agent, 30-65 parts of dibasic acid, 0.02-0.06 part of dispersing agent, 0.03-0.15 part of catalyst and 0.03-0.1 part of stabilizer. The high-whiteness film provided by the invention has better whiteness by optimizing the types of branching agents and stabilizing agents, and is less prone to yellowing caused by high temperature and ultraviolet erosion. And the polyester film has better tensile strength and tear resistance by optimizing the type of the branching agent and the weight ratio of the dibasic acid to the dibasic alcohol, so that the breakage caused by stretching can be reduced in the using process, the coated object can be stably contacted with the polyester film, and a better protection effect is realized.
Description
Technical Field
The invention relates to a high-whiteness film and a preparation method thereof, mainly relates to C08, and particularly relates to the field of organic high molecular compounds.
Background
With the improvement of living standard, the quality requirement of people on living environment is higher, white pollutants greatly influence the living quality of people, but because the convenient use performance of polyester products makes the polyester products indispensable in our production life, the development of biodegradable polyester is very important. The patent CN200810200964.5 is complicated in operation process by adding polyethylene glycol as a branching agent and adding a color stabilizer to eliminate color change caused by titanate catalyst. The patent CN201811295682.8 can improve the degradability of the polyester film by adding PHA modified polyester film, but may cause the reduction of impact performance and whiteness.
Disclosure of Invention
In order to improve biodegradability and whiteness of the polyester film, the first aspect of the invention provides a high-whiteness film, which is prepared from the following raw materials in parts by weight: 30-60 parts of terephthalic acid, 40-55 parts of 1, 4-butanediol, 0.02-0.1 part of branching agent, 30-65 parts of dibasic acid, 0.02-0.6 part of dispersing agent, 0.03-0.15 part of catalyst and 0.03-0.1 part of stabilizer.
As a preferred embodiment, the branching agent is an amine derivative comprising one of the following structures- (OH) m-R1- (NH) n-, R1- (NH) n, R1 is CH 2 And m + n is 2 to 10.
In a preferred embodiment, the branching agent is selected from one or more of stearic acid diethanolamine, stearic acid triisopropanolamine, diglycolamine, triethanolamine, diisopropanolamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
As a preferred embodiment, the branching agents are triisopropanolamine monostearate and diethylenetriamine.
Further preferably, the weight ratio of triisopropanolamine monostearate to diethylenetriamine is 1: (0.5-1).
As a preferred embodiment, the weight ratio of terephthalic acid to 1, 4-butanediol and triisopropanolamine monostearate is 1: (0.8-1.5): (0.035-0.175).
The applicant finds that in the experimental process, when the branching agent is triisopropanolamine monostearate and diethylenetriamine, a polyester film with higher whiteness can be obtained, and the polyester film has better mechanical property and thermal stability. The possible reasons for guessing are: triisopropanolamine monostearate and diethylenetriamine are innovatively adopted as branching agents, an amide group can be formed, the thermal stability of the high-whiteness film can be better improved, the absorption of the polyester film to visible light can be effectively reduced by introducing the amide group, the reflection efficiency of the polyester film to the visible light is improved, and due to the high reactivity of the amide group and the stability of the group, the thermal degradation of the material is reduced, so that higher whiteness can be realized. And applicants further found that when the weight ratio of terephthalic acid to 1, 4-butanediol and triisopropanolamine monostearate was 1: (0.8-1.5): (0.035 to 0.175), triisopropanolamine monostearate can form a stable network cross-linking structure with terephthalic acid and 1, 4-butanediol, so that the mechanical property of the high-whiteness film can be improved, and the high-whiteness film has good tensile strength and is not easy to damage.
As a preferred embodiment, the dibasic acid is selected from one or more of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
As a preferred embodiment, the dibasic acids are succinic acid and adipic acid.
More preferably, the weight ratio of the succinic acid to the adipic acid is (5-8): 1.
the applicant finds in the experimental process that the dibasic acid is preferably the compound of succinic acid and adipic acid, and the weight ratio is (5-8): 1, the tensile strength and the impact resistance of the prepared polyester film can be improved.
As a preferred embodiment, the dispersing agent is selected from one or a combination of several of zinc stearate, calcium stearate and barium stearate.
In a preferred embodiment, the diffusing agent is zinc stearate.
As a preferred embodiment, the catalyst is selected from one or more of isopropyl titanate, tetraisopropyl titanate, n-butyl titanate, tetrabutyl titanate, alkyl titanic acid and tetra-tert-butyl titanate.
As a preferred embodiment, the molar ratio of the dibasic acid to 1, 4-butanediol is 1: (1-3).
As a preferred embodiment, the stabilizer is one or more selected from calcium phosphate, sodium phosphate, potassium phosphate, trimethyl phosphate, triphenyl phosphate and phosphorous acid.
As a preferred embodiment, the stabilizer is calcium phosphite.
As a preferred embodiment, the weight ratio of zinc stearate to calcium phosphite is 1: (1-2).
In the experimental process, the applicant finds that zinc stearate is selected as a dispersing agent, calcium phosphite is selected as a stabilizing agent, and the weight ratio of the zinc stearate to the calcium phosphite is 1: when the compound (1-2) is used, the surface properties of the high-whiteness film can be improved, and the apparent gloss of the film can be improved.
The second aspect of the present invention provides a method for preparing a high-whiteness film, comprising the steps of:
(1) adding terephthalic acid, 1, 4-butanediol, dibasic acid, a branching agent and a catalyst into a reaction kettle for esterification;
(2) firstly, carrying out a pre-polycondensation reaction under reduced pressure, adding a catalyst, a dispersing agent and a stabilizing agent, and then continuously carrying out a polycondensation reaction under reduced pressure;
(3) and (3) carrying out blow molding on the mixture obtained in the step (2) to form a film, thus obtaining the high-whiteness film.
As a preferred embodiment, the temperature during the esterification reaction is 200-250 ℃ and the temperature during the pre-polycondensation and polycondensation reactions is 230-250 ℃.
As a preferred embodiment, nitrogen is introduced for protection during the esterification reaction, the pressure during the pre-polycondensation reaction is 7-10kPa, and the pressure during the polycondensation reaction is 100-200 Pa.
As a preferred embodiment, the amount of the catalyst added in the esterification reaction is 0.05 to 0.1 part, and the amount of the catalyst added in the polycondensation reaction is 0.1 to 0.15 part.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-whiteness film provided by the invention has better whiteness by preferably selecting the branching agent and stabilizing agent, and yellowing is less likely to occur even after the high-whiteness film is corroded by high temperature and ultraviolet rays.
(2) According to the high-whiteness film, the polyester film has better tensile strength and tear resistance by optimizing the type of the branching agent and the weight ratio of the dibasic acid to the dibasic alcohol, so that the breakage caused by stretching can be reduced in the using process, a coated object can be stably contacted with the polyester film, and a better protection effect is realized.
(3) The high-whiteness film disclosed by the invention has good biodegradability, can be degraded through compost, and reduces the white pollution of the polyester film to the environment.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, all starting materials used are commercially available, unless otherwise specified.
Example 1
A high-whiteness film is prepared from the following raw materials in parts by weight: 45 parts of terephthalic acid, 47.5 parts of 1, 4-butanediol, 0.08 part of branching agent, 47.5 parts of dibasic acid, 0.05 part of dispersing agent, 0.15 part of catalyst and 0.05 part of stabilizer.
The branching agent is triisopropanolamine monostearate and diethylenetriamine, and the weight ratio is 1: 0.75.
the dibasic acid is succinic acid and adipic acid, and the weight ratio is 5: 1.
the dispersing agent is zinc stearate. The catalyst is tetrabutyl titanate.
The stabilizer is calcium phosphite.
A preparation method of a high-whiteness film comprises the following steps:
(1) adding terephthalic acid, 1, 4-butanediol, dibasic acid, a branching agent and a catalyst into a reaction kettle for esterification reaction at 225 ℃ for 3 hours;
(2) carrying out a pre-polycondensation reaction for 2h under reduced pressure, adding a catalyst, a dispersing agent and a stabilizing agent, and then continuously carrying out the polycondensation reaction for 2h under reduced pressure, wherein the temperature in the pre-polycondensation and polycondensation reaction processes is 240 ℃, the pressure in the pre-polycondensation reaction process is 8kPa, and the pressure in the polycondensation reaction process is 150 Pa;
(3) and (3) carrying out blow molding on the mixture obtained in the step (2) to form a film, thus obtaining the high-whiteness film.
The amount of the catalyst added in the esterification reaction was 0.05 part, and the amount of the catalyst added in the polycondensation reaction was 0.1 part.
Example 2
A high-whiteness film is prepared from the following raw materials in parts by weight: 50 parts of terephthalic acid, 40 parts of 1, 4-butanediol, 0.04 part of branching agent, 30 parts of dibasic acid, 0.04 part of dispersing agent, 0.1 part of catalyst and 0.06 part of stabilizing agent.
The branching agent is triisopropanolamine monostearate and diethylenetriamine, and the weight ratio is 1: 0.6.
the dibasic acid is succinic acid and adipic acid, and the weight ratio is 8: 1.
the dispersing agent is calcium stearate. The catalyst is tetrabutyl titanate.
The stabilizer is zinc phosphite.
A preparation method of a high-whiteness film comprises the following steps:
(1) adding terephthalic acid, 1, 4-butanediol, dibasic acid, a branching agent and a catalyst into a reaction kettle for esterification reaction at the temperature of 200 ℃ for 4 hours;
(2) carrying out a pre-polycondensation reaction for 3 hours under reduced pressure, adding a catalyst, a dispersing agent and a stabilizing agent, and then continuously carrying out a polycondensation reaction for 3 hours under reduced pressure, wherein the temperature in the pre-polycondensation and polycondensation reaction processes is 230 ℃, the pressure in the pre-polycondensation reaction process is 10kPa, and the pressure in the polycondensation reaction process is 200 Pa;
(3) and (3) carrying out blow molding on the mixture obtained in the step (2) to form a film, thus obtaining the high-whiteness film.
The amount of the catalyst added in the esterification reaction was 0.65 parts, and the amount of the catalyst added in the polycondensation reaction was 0.35 parts.
Example 3
A high whiteness film and a method for preparing the same, comprising the same steps as in example 1, except that the branching agent is pentaerythritol.
Example 4
The specific steps of a high-whiteness film and a preparation method thereof are the same as those of example 1, and the difference is that the weight ratio of terephthalic acid to 1, 4-butanediol to stearic acid triisopropanolamine is 1: 1: 0.2.
example 5
A high-whiteness film and a method for producing the same, which comprises the same specific steps as in example 1, except that the weight ratio of terephthalic acid to 1, 4-butanediol to triisopropanolamine monostearate is 1: 1: 0.02.
performance testing
1. Whiteness: the reflectance of the polyester film to light at a wavelength of 457nm was measured by an ultraviolet spectrophotometer model U-3900 of HITACHI, Japan, and the whiteness of the polyester film was reflected.
2. Impact strength: the impact resistance of the polyester film prepared was tested according to GB/T1040.3-2006 standard, and the following data is the impact strength before breaking.
3. Tensile strength: the tensile strength of the polyester film prepared was tested according to the GB 13022-1991 standard.
Examples 1-5 were tested according to the above criteria and the results are given in table 1.
TABLE 1
| Whiteness/% | Impact resistance kJ/m 2 | Tensile Strength/kPa | |
| Example 1 | 95.5 | 13.8 | 32.5 |
| Example 2 | 94.3 | 13.6 | 31.3 |
| Example 3 | 89.5 | 13.1 | 26.4 |
| Example 4 | 88.6 | 13.3 | 27.1 |
| Example 5 | 89.1 | 13.2 | 25.9 |
Claims (10)
1. The high-whiteness film is characterized by comprising the following preparation raw materials in parts by weight: 30-60 parts of terephthalic acid, 40-55 parts of 1, 4-butanediol, 0.02-0.1 part of branching agent, 30-65 parts of dibasic acid, 0.02-0.06 part of dispersing agent, 0.03-0.15 part of catalyst and 0.03-0.1 part of stabilizer.
2. The high whiteness film of claim 1 wherein the branching agent is an amine derivative comprising one of the following structures- (OH) m-R1- (NH) n-, R1- (NH) n, and R1 is CH 2 And m + n is 2 to 10.
3. The high whiteness film of claim 1 wherein the branching agent is selected from one or more of diglycolamine, triethanolamine, diisopropanolamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, triisopropanolamine monostearate, and diethanolamine stearate.
4. The high whiteness film of claim 1 wherein the weight ratio of terephthalic acid to 1, 4-butanediol to branching agent is from 1: (0.8-1.5): (0.035-0.175).
5. The high whiteness film according to claim 1, wherein the dibasic acid is selected from one or more of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
6. The high whiteness film according to claim 1, wherein the diffusing agent is selected from one or more of zinc stearate, calcium stearate and barium stearate.
7. The high whiteness film of claim 1 wherein the catalyst is selected from one or more of isopropyl titanate, tetraisopropyl titanate, n-butyl titanate, tetrabutyl titanate, alkyl titanic acid, and tetra-tert-butyl titanate.
8. The high whiteness film of claim 1, wherein the molar ratio of the dibasic acid to 1, 4-butanediol is from 1: (1-3).
9. The high whiteness film according to claim 1, wherein the stabilizer is one or more selected from calcium phosphate, sodium phosphate, potassium phosphate, trimethyl phosphate, triphenyl phosphate, and phosphorous acid.
10. A method for preparing a high whiteness film according to any one of claims 1 to 9, comprising the steps of:
(1) adding terephthalic acid, 1, 4-butanediol, dibasic acid, a branching agent and a catalyst into a reaction kettle for esterification;
(2) carrying out a pre-polycondensation reaction under reduced pressure, adding a catalyst, a dispersant and a stabilizer, and then continuously carrying out the polycondensation reaction under reduced pressure;
(3) and (3) carrying out blow molding on the mixture obtained in the step (2) to form a film, thus obtaining the high-whiteness film.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479116A (en) * | 2014-12-04 | 2015-04-01 | 金发科技股份有限公司 | Preparation method of poly-terephthalic acid isophthalic acid adipic acid/ butanediol copolyester |
| CN112759747A (en) * | 2021-02-04 | 2021-05-07 | 新疆蓝山屯河聚酯有限公司 | Poly (butylene sebacate-butylene terephthalate) and preparation method thereof |
| CN112920388A (en) * | 2021-01-27 | 2021-06-08 | 唐山睿安科技有限公司 | Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479116A (en) * | 2014-12-04 | 2015-04-01 | 金发科技股份有限公司 | Preparation method of poly-terephthalic acid isophthalic acid adipic acid/ butanediol copolyester |
| CN112920388A (en) * | 2021-01-27 | 2021-06-08 | 唐山睿安科技有限公司 | Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
| CN112759747A (en) * | 2021-02-04 | 2021-05-07 | 新疆蓝山屯河聚酯有限公司 | Poly (butylene sebacate-butylene terephthalate) and preparation method thereof |
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