CN111471297B - Preparation method and application of bio-based transparent polyamide - Google Patents
Preparation method and application of bio-based transparent polyamide Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 69
- 229920002647 polyamide Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002028 Biomass Substances 0.000 claims abstract description 24
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003287 optical effect Effects 0.000 claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 12
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 12
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 12
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 7
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 230000003179 granulation Effects 0.000 claims abstract description 5
- 238000005469 granulation Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000004806 packaging method and process Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 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
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 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
- 239000000463 material Substances 0.000 abstract description 21
- 238000006116 polymerization reaction Methods 0.000 abstract description 17
- 239000000178 monomer Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000004677 Nylon Substances 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl diamine Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920006021 bio-based polyamide Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/166—Magnesium halide, e.g. magnesium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses a preparation method and application of bio-based transparent polyamide, and the transparent polyamide is polymerized from biomass-derived monomers, the polymerization process is simple, the energy consumption is low, and the obtained polyamide has excellent mechanical properties and optical properties. The method comprises the following steps: adding 2,5-furandicarboxylic acid from biomass, pentamethylene diamine, diamine from biomass, benzoic acid and butanol solvent into a reaction kettle, raising the reaction temperature to 150-180 ℃, and continuously maintaining the reaction to obtain white solid powder. And adding metal salt and the epoxidized cardanol derived from biomass into the obtained solid powder, and performing reaction extrusion and granulation in a double-screw extruder to obtain the bio-based transparent polyamide. The bio-based transparent polyamide material has excellent optical performance, high impact strength, chemical solvent resistance and stress cracking resistance, and is particularly suitable for application fields of optical lenses, protective glasses, packaging outer boxes and the like.
Description
Technical Field
The invention relates to the field of polyamide materials, in particular to a preparation method and application of bio-based transparent polyamide.
Background
The polyamide as engineering plastic has the characteristics of high mechanical property, high impact property, high heat resistance, good chemical resistance, easy forming and the like, and is widely applied to the fields of automobiles, electronic and electric appliances and the like. However, polyamide has low transparency, and is difficult to play a material role in some application fields with high requirements on material transparency. Therefore, a great deal of work is carried out by domestic and foreign research institutes to prepare polyamide materials with high transparency.
In the prior art, transparent polyamides include mainly aliphatic transparent polyamides, aromatic transparent polyamides and semi-aromatic transparent polyamides. The Chinese patent application with the application number of 201510837538.2 (the publication number CN 105367785) discloses a transparent nylon and a preparation method thereof, wherein the transparent nylon contains branched chain alkyl diamine and oxalic acid units. Chinese patent publication No. (CN 107286340a, application No. 201710624544.9) discloses a copolymerized transparent nylon and its synthesis method, the transparent nylon raw material includes lactam, alicyclic diamine, long carbon chain dibasic acid and cyclohexane dibasic acid. Chinese patent application publication No. (CN 110092906a, application No. 201910467801.1) discloses a copolymerized transparent nylon comprising terephthalic acid or isophthalic acid, aliphatic dibasic acid and alicyclic dibasic acid, and a method for preparing the same. The Chinese patent application with publication number (CN 107286340A, application number 201710624544.9) discloses a copolymerized transparent nylon and a preparation method thereof, wherein the copolymerized transparent nylon is mainly prepared by polycondensation of a component A and a component B: wherein the component A is prepared by polymerizing aromatic dibasic acid and 2-methyl pentanediamine; the component B is salt polymerized by diamino siloxane and aliphatic dibasic acid. Chinese patent publication No. (CN 105330852A, application No. 201510888557.8) discloses a bio-based long carbon chain transparent nylon and a synthesis method thereof, the transparent nylon is copolymerized by a monomer 1 and polyesteramide, the monomer 1 is composed of decamethylenediamine, m-phenylenediamine and adipic acid with the molar ratio of 1. Transparent polyamide is generally an amorphous material, the random copolyparameric structure regularity of aliphatic diacid and diamine is damaged limitedly, the polyamide is crystallized faster, and the transparency is closely related to the processing conditions. Due to the existence of aromatic monomers, the polymerization process is relatively difficult, and the problems of decarboxylation, branching, color change and the like exist in the polymerization process, so that the optical performance of the polyamide is influenced. Therefore, there is a need for continued improvement in the polymerization process thereof. On the other hand, most of transparent polyamides are synthesized by polymerization of petroleum-based monomers such as terephthalic acid and hexamethylenediamine, but nowadays, sustainable transparent polyamides can be synthesized from renewable resources facing the problems of petroleum resource consumption, waste discharge and energy consumption.
Disclosure of Invention
In order to solve the problem that petroleum of transparent polyamide is used as a non-renewable material of a raw material and improve the problems of complex process, high energy consumption and the like in the polymerization process of the transparent polyamide, the invention provides the bio-based transparent polyamide, the transparent polyamide is polymerized by biomass-derived monomers, the polymerization process is simple, the energy consumption is low, and the obtained polyamide has excellent mechanical properties and optical properties.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of bio-based transparent polyamide comprises the following steps:
(1) Adding 2,5-furandicarboxylic acid from biomass, pentamethylene diamine, diamine from biomass, benzoic acid and butanol into a reaction kettle, introducing protective gas for replacement and discharging air in the kettle, firstly heating the reaction kettle until the butanol flows back, then discharging and recovering the butanol, raising the reaction temperature to 150-180 ℃, continuously keeping the reaction for 10-90 min, and obtaining white solid powder after the reaction is finished;
(2) And (2) adding metal salt and epoxidized cardanol from biomass into the solid powder obtained in the step (1), and performing reaction extrusion and granulation in a double-screw extruder to obtain the bio-based transparent polyamide.
In the step (1), the type of the diamine derived from biomass is Croda Heda
1075, the chemical formula is:
the reaction temperature is increased to 160-170 ℃, and the reaction is continuously kept for 45-65 min.
The protective gas is nitrogen.
Heating by microwave until butanol refluxes. The power of the microwave heating is 600w-1200w, most preferably 800w
Reflux is maintained for 5-30min, most preferably 20min.
The butanol is then recovered by evacuation through a vacuum pump.
In the step (1), the following raw materials in parts by weight are adopted:
the weight ratio of the pentamethylene diamine to the biomass source diamine is 50-80: 100, more preferably 55 to 65:100.
in the step (2), the weight part ratio of the metal salt, the epoxidized cardanol and the 2,5-furandicarboxylic acid in the step 1) is 0.1-2 parts: 1-5 parts of: 30-80 parts of
The metal salt is one or more than two of magnesium chloride, calcium chloride, magnesium phosphate and calcium phosphate.
The epoxy value of the epoxidized cardanol is 4.1-4.6%.
The reaction extrusion temperature of the double-screw extruder is 190-260 ℃.
The invention has the innovation points that bio-based furan dicarboxylic acid, pentanediamine and diamine derived from biomass are adopted
1075 as a polymerization monomer, the wholly bio-based polyamide is obtained by polymerization. By adjusting the source of the diamine
1075 the monomer content, and the regularity of the polyamide chain segment is adjusted, thereby improving the transparency of the polyamide. In order to further regulate and control the motion capability of the polyamide chain segment, the biological epoxy cardanol is adopted to carry out micro-crosslinking on the polyamide chain, so that the crystallization capability of the polyamide material is limited. In addition, by adding metal ions, the chelation between the metal ions and the amide groups is utilized to reduce the intermolecular action of the polyamide, thereby obtaining the polyamide with high transparency and high strength. In a polymerization processIn the method, the traditional electric heating mode is replaced by microwave rapid heating, and the microwave and monomer molecules act to realize rapid and uniform heating on one hand, reduce the activation energy of polymerization reaction, reduce the polymerization reaction temperature and shorten the reaction time on the other hand, thereby improving the comprehensive properties such as transparency of the polyamide obtained by polymerization.
The bio-based transparent polyamide material meets the requirements of green renewable materials of bio-based sources. The bio-based transparent polyamide material has excellent optical performance, high impact strength, chemical solvent resistance and stress cracking resistance, and is particularly suitable for application fields of optical lenses, protective glasses, packaging outer boxes and the like.
Most preferably, a method for preparing a bio-based transparent polyamide comprises the following steps:
(1) Adding 2,5-furandicarboxylic acid from biomass, pentamethylene diamine, diamine from biomass, benzoic acid and butanol into a reaction kettle, wherein the diamine from biomass is produced by Croda Heda
1075, introducing protective gas to replace and exhaust air in the kettle, heating the reaction kettle by microwave until butanol flows back, keeping the flow back for 20min at the microwave heating power of 800w, then exhausting and recovering butanol, raising the reaction temperature to 165 ℃, continuing to keep reacting for 55min, and obtaining white solid powder after the reaction is finished;
(2) And (2) adding calcium chloride and epoxidized cardanol derived from biomass into the solid powder obtained in the step (1), and performing reaction extrusion and granulation in a double-screw extruder to obtain the bio-based transparent polyamide.
The method adopts the following raw materials in parts by weight:
the bio-based transparent polyamide obtained by the method has the relative viscosity of 2.6, the tensile strength of 69MPa and the Charpy notch impact of 18.0kJ/m 2 The light transmittance is 92.1%, the haze is 1.9%, and the film has very excellent performance.
Compared with the prior art, the invention has the following advantages:
the bio-based transparent polyamide of the invention adopts furandicarboxylic acid as dibasic acid, pentanediamine and
1075 As the diamine, use is made of
1075 regulating and controlling the regularity of polyamide material, so as to obtain the transparent polyamide material based on total organism. The biological epoxy cardanol is added for micro-crosslinking, so that the movement capability of a molecular chain segment is reduced, the strength and toughness of the material are improved, the chelating effect is generated between the compounded metal ions and the polyamide, and the crystallization performance and mechanical strength of the polyamide are further reduced.
The bio-based transparent polyamide polymerization engineering replaces the traditional electric heating to heating mode by the microwave radiation heating mode, so that the polymerization reaction temperature and time are reduced, the heating uniformity in the polymerization process is realized, the occurrence of side reactions in the polymerization process is greatly reduced, and the optical performance of the polyamide material is improved.
Drawings
FIG. 1 is a DSC curve of bio-based transparent polyamide obtained in example 3 of the present invention.
Detailed Description
The invention will now be further illustrated by reference to the following examples:
2,5-Furan dicarboxylic acid (Shanghai Xun Technique Co., ltd.), pentanediamine (Kaiser Biotech),
1075 (Croda), butanol (alatin reagent), benzoic acid (alatin reagent), magnesium chloride (alatin reagent), epoxy cardanol (Ayaobao biomaterial Co., ltd., epoxy value of 4.1-4.6%)
The preparation method of the bio-based transparent polyamide comprises the following steps of:
(1) Mixing 2,5-furandicarboxylic acid (30-80 parts) derived from biomass, pentamethylenediamine, diamine (derived from biomass), (b) and (c)
1075, croda), benzoic acid (0.1 to 5 parts) and butanol (300 parts) as a solvent are added into a reaction kettle, and nitrogen is introduced to replace and exhaust air in the kettle. Firstly, heating a reaction kettle in a microwave mode until butanol refluxes, keeping for 20min, then discharging and recovering the butanol through a vacuum pump, raising the reaction temperature to 165 ℃, continuously keeping the reaction for 55min, and obtaining white solid powder after the reaction is finished.
(2) And (2) adding magnesium chloride and epoxidized cardanol derived from biomass into the solid powder obtained in the step (1), and performing reaction extrusion and granulation in a double-screw extruder (the reaction extrusion temperature is 210-250 ℃) to obtain the bio-based transparent polyamide.
The DSC curve of the bio-based transparent polyamide obtained in the example 3 of the invention is shown in figure 1, the polyamide material has no obvious melting peak in the temperature rise process, and the Tg is about 125 ℃.
Infrared spectrum (IR v/cm) of bio-based transparent polyamide obtained according to example 3 of the present invention -1 ) Obtained, amide group NH absorption peaks appeared at 3350 and 1570; a furan ring CH structure peak at 3180; furan ring = C-O-C = absorption peaks at 1050 and 1230; an absorption peak belonging to furan ring C = C appears at 1540; a peak belonging to the amide bond C = O structure appears at 1664; the C-N absorption peak appears at 1340; in the carbon Chain (CH) at 720 2 ) n Structural peaks, indicating that the final product was a polyamide.
The test method comprises the following steps:
(1) Relative viscosity of sulfuric acid
The relative viscosity of a polyamide having a concentration of 0.1g/ml is measured in concentrated sulfuric acid at 25 DEG C
(2) Physical and mechanical properties
The prepared polyamide material was injection molded into dumbbell-shaped specimens, which were tested for tensile strength and notched impact strength according to the ISO standard.
(3) Optical Properties
Light transmittance and haze the optical properties of the 2mm square plaques were measured by a haze meter.
The results of the tests are shown in table 2.
Examples 1 to 3 and comparative examples 1 to 2
The material proportions of examples 1 to 3 and comparative examples 1 to 2 are shown in Table 1, and the numerical values in Table 1 are in parts by weight.
TABLE 1
TABLE 2
| Item | Unit of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Relative viscosity | 1.9 | 2.2 | 2.6 | 1.2 | 1.4 | |
| Tensile strength | MPa | 58 | 63 | 69 | 61 | 52 |
| Charpy notched impact | kJ/m 2 | 13.5 | 16.3 | 18.0 | 6.7 | 11.8 |
| Light transmittance | ％ | 84.2 | 89.3 | 92.1 | 82 | 75 |
| Haze (haze) | ％ | 4.5 | 3.3 | 1.9 | 10.2 | 27.5 |
The polyamide materials obtained in examples 1 to 3 have excellent optical properties and toughness.
From examples 1, 2 and comparative example 2, the optical properties of examples 1, 2 are superior to comparative example 2, and the relative viscosity and impact strength of examples 1, 2 are higher because the polyamide is micro-crosslinked through the epoxy group of cardanol, and the polyamide crystallization rate is further decreased. Compared with the comparative example 1, in the comparative example 1, the polyamide obtained by adopting the ordinary electric heating way for reaction has low relative viscosity, so that the notch impact of the material is low, and the polyamide undergoes obvious oxidative degradation in the ordinary heating reaction process, so that the optical property of the material is poor.
The above description is only an embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modifications made by using the design concept should fall within the scope of infringing the present invention.
Claims (6)
1. The preparation method of the bio-based transparent polyamide is characterized by adopting the following raw materials in parts by weight:
30-80 parts of 2,5-furandicarboxylic acid from biomass;
10-30 parts of pentamethylene diamine;
20-45 parts of diamine derived from biomass;
200-400 parts of butanol;
0.1-5 parts of benzoic acid;
0.1-2 parts of metal salt;
1-5 parts of epoxidized cardanol;
the preparation method comprises the following steps:
(1) Adding 2,5-furandicarboxylic acid from biomass, pentamethylene diamine, diamine from biomass, benzoic acid and butanol into a reaction kettle, introducing protective gas for replacement and discharging air in the kettle, firstly heating the reaction kettle in a microwave mode until the butanol flows back, then discharging and recovering the butanol, raising the reaction temperature to 150-180 ℃, continuously keeping the reaction for 10-90 min, and obtaining white solid powder after the reaction is finished;
the chemical structural formula of the diamine derived from biomass is as follows:
(2) Adding metal salt and epoxidized cardanol derived from biomass into the solid powder obtained in the step (1), and performing reaction extrusion and granulation in a double-screw extruder to obtain bio-based transparent polyamide;
the metal salt is one or more than two of magnesium chloride, calcium chloride, magnesium phosphate and calcium phosphate.
2. The method for preparing bio-based transparent polyamide as claimed in claim 1, wherein in step (1), the protective gas is nitrogen.
3. The method for preparing bio-based transparent polyamide as claimed in claim 1, wherein the power of microwave heating in step (1) is 600w-1200w.
4. The method for preparing bio-based transparent polyamide as claimed in claim 1, wherein in the step (1), the reaction temperature is raised to 160 ℃ to 170 ℃, and the reaction is continuously maintained for 45min to 65min.
5. The method for preparing bio-based transparent polyamide as claimed in claim 1, wherein the reflux is maintained for 5 to 30min in step (1).
6. Use of a bio-based transparent polyamide prepared according to the preparation method of any one of claims 1~5 in the preparation of optical lenses, goggles and packaging boxes.
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