CN102850541A - Biomass based polyamide resin - Google Patents
Biomass based polyamide resin Download PDFInfo
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- CN102850541A CN102850541A CN 201110195434 CN201110195434A CN102850541A CN 102850541 A CN102850541 A CN 102850541A CN 201110195434 CN201110195434 CN 201110195434 CN 201110195434 A CN201110195434 A CN 201110195434A CN 102850541 A CN102850541 A CN 102850541A
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Abstract
The invention discloses a biomass-based semi-aromatic polyamide copolymer having the advantages of excellent thermal property and low water absorption rate. The biomass-based polyamide resin contains a furan diacid unit (a), a terephthalic acid unit (b), a biomass-based 1,10-decamethylene diamine unit (c), and an aliphatic diamine unit (c) with the carbon number of above 4 except the unit (c), wherein the content of the unit (a) is 50-98mol% of the total amount of the unit (a) and the unit (b), and the content of the unit (d) is 0-30mol% of the total amount of the unit (c) and the unit (d). The copolymer has excellent physical and mechanical performance, can be used in engineering plastics, and also can be used in other industrial materials and materials for manufacturing electrical and electronic devices.
Description
Technical field
The present invention relates to a kind of polyamide resin, be specifically related to a kind of biomass-based semiaromatic polyamide composition with good calorifics mechanical property.
Background technology
Raw material as polyamide resin, used this so-called fossil feedstock of oil in the past, but in order to prevent global warming and structure Circular Society Construction by the discharging that suppresses carbonic acid gas, the manufacturing raw material of expectation polyamide resin replaces with the raw material of authigenic material.
The polyamide resin of making as the raw material that uses authigenic material, known have nylon-11 and a PA-12.They have good character, resistance to chemical corrosion for example, and good snappiness, and dimensional stabilizing etc., but its apparent in view defective is that relatively poor thermomechanical property is (referring to patent documentation: CN1214349).
The biomass material that makes and the nylon-56 made are compared with nylon-6 or nylon-66, have roughly equal thermotolerance and mechanical and physical performance, cause poor dimensional stability but its open defect is high-hygroscopicity.It stops poor heat stability, the resin that stops thermally-stabilised difference be unsuitable for such as the long large-scale products formed of the shaping cycles such as resin air intake branch of trolley part (referring to references: CN101442382A)
For above-mentioned reasons, good thermal property and the biological poly amide resins of agent of low hygroscopicity appear in expectation.
Summary of the invention
Be the friendly materials problem of the native to this world environment of raw material for the oil that solves polymeric amide, and the problems such as good thermomechanical property and low rate of moisture absorption, the invention provides a kind of biomass-based semiaromatic polyamide composition that good calorifics mechanical property is arranged, and this semiaromatic polyamide composition has excellent mechanical property, and is the friendly materials of global environment.
The present invention is a kind of biomass-based polyamide resin that contains, and this contains biomass-based polyamide resin and contains:
(a) furans diprotic acid unit,
(b) terephthalic acid units,
(c) biomass-based 1，10-diaminodecane unit,
(d) (c) carbonatoms beyond the unit is binary aliphatic amine unit more than 4;
Wherein (a) unit content is (a) unit and (b) 50mol%～98mol% of the total amount of unit, and (d) unit content be (c) unit and (d) 0mol%～30mol% of the total amount of unit.
Above-mentioned (a) unit content is considered the reasons such as thermal property of polymkeric substance, is chosen as (a) unit and (b) 50mol%～98mol% of the total amount of unit.When (a) unit content is lower than 50mol%, this fusing point that contains biomass-based polyamide resin will be higher than 290 ℃, and this biomass content that contains biomass-based polyamide resin will reduce, will cause like this this polymeric amide at the forming process excess Temperature thermal destruction and gelation to occur easily, and cause losing good mechanical properties and good chemical resistance.When (a) unit content was higher than 98mol%, this second-order transition temperature that contains biomass-based polyamide resin can reduce, and caused this polyamides dimensional stabilizing variation.
Above-mentioned (d) unit content is considered the reasons such as the thermal property of polymkeric substance and rate of moisture absorption, is chosen as (c) unit and (d) 0mol%～30mol% of the total amount of unit.When (d) unit content is higher than 30mol%, this fusing point that contains biomass-based polyamide resin will be lower than 220 ℃, and this second-order transition temperature that contains biomass-based polyamide resin will reduce rapidly, will cause like this this polymeric amide to lose good dimensional stability, good mechanical properties and good chemical resistance.
Consider more excellent thermal property and the dimensional stability of polymkeric substance, (d) (c) the carbonatoms element beyond the unit be 4 or more the binary aliphatic amine unit with respect to (c) biomass-based 1，10-diaminodecane unit and (d) (c) unit carbonatoms element in addition be that the molar content of the binary aliphatic amine unit total amount more than 4 is preferably 0mol%-25mol%.
Environment friendly is considered in above-mentioned (a) furans diprotic acid unit, is preferably the furans diprotic acid unit of bio-based monomer.Consider the reasons such as thermal property of raw materials cost and polymkeric substance, furans-2,5 dioctyl phthalate, 3 more preferably, 4-dimethoxy furans-2, one or more in 5-dioctyl phthalate or furans-3,4 dioctyl phthalate.And be preferably furans-2,5-dioctyl phthalate.
Furans-2,5-dioctyl phthalate unit is from Mierocrystalline cellulose or xylogen etc.The main process of preparation is hydrocellulose or xylogen generation hexose (glucose and fructose) under acidic conditions, and hexose and then dehydration generate 5 hydroxymethyl furfural.By the synthetic furans-2 of hydroxymethylfurfural oxidation, 5-dioctyl phthalate.
Above-mentioned (d) (c) carbonatoms beyond the unit is binary aliphatic amine unit more than 4, considers the reasons such as low rate of moisture absorption of raw materials cost and polymkeric substance, be preferably carbonatoms and be 4～18 the straight chain diamine in one or more.Be preferably Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octane diamines, 1,9-nonane diamine, 1,11-undecane diamines, 1,12-dodecane diamines, 1,13-tridecane diamines, 1,14-tetradecane diamines, 1,15-pentadecane diamines, 1,16-n-Hexadecane diamines, 1,17-heptadecane diamines, 1,18-octadecamethylene diamine, 2-methyl isophthalic acid, 8-octane diamines or 5-methyl isophthalic acid, one or more in the 9-nonane diamine.
Above-mentioned (c) biomass-based 1，10-diaminodecane unit is from Viscotrol C.The main process of preparation is the sebacic acid from Viscotrol C to be carried out the ammonification Dehydration get binary cyanogen, then this binary cyanogen carried out that Hydrogenation gets.Can improve thus biological substance than (from raw material shared ratio in the employed raw material of polyamide resin of biological substance).Biological substance among the present invention is than referring to raw material from biological substance shared ratio in the raw material of polyamide resin, and it can represent by following formula: biological substance is than (%)=100 * from the weight of raw materials of the weight of the raw material of biological substance/all.
The biomass-based polyamide resin that contains among the present invention has following characteristics: fusing point is 220 ℃～290 ℃, and second-order transition temperature is 80 ℃～110 ℃, and 25 ℃ of saturated water absorptions are 4.0%～7.0%.
This contains in the preparation of biomass-based polyamide resin can optionally use the additives such as molecular weight regulator, stablizer.Molecular weight regulator can make monocarboxylic acid or monoamine, and monocarboxylic consumption is generally the 0.05-5wt% of di-carboxylic acid total amount, and it is 0.05-5wt% that the consumption of monoamine is generally the diamine total amount.The monocarboxylic acid of molecular weight regulator can be selected from aliphatic monocarboxylic acid or aromatic monocarboxylate or alicyclic monocarboxylic acid, and monoamine can be selected from aliphatics monoamine or alicyclic monoamine or aromatic series monoamine.Stablizer can be selected from Hypophosporous Acid, 50, phosphorous acid, phosphoric acid, phosphite, hypophosphite or phosphoric acid salt, and its consumption is generally the 0.1-0.5wt% of total charging capacity.
The present invention is not particularly limited for the above-mentioned preparation method who contains biomass-based polyamide resin, can use above-mentioned diprotic acid, diamine and a certain amount of additive to add to according to a certain percentage in the general nylon polymeric kettle, then begin to heat to 160 ℃～260 ℃, pressure maintains under 1.0MPa～2.5MPa condition and reacted 2 hours～5 hours, then begin to be decompressed to normal pressure, the prepolymer that obtains carries out drying, pulverizing.Vacuum solid state reaction under 200 ℃～280 ℃ temperature.
Obtain polymeric amide among the present invention and have good thermomechanical property, high resistance to chemicals medicine and very good mechanical properties.Owing to having this type of excellent properties, polymeric amide itself or the optional various additives of using with various polymeric amide are combined with other polymkeric substance and can be carried out molding or spinning with composition forms, make various goods or fiber.Moulded parts and spinning fibre have many purposes, not only are used for engineering plastics, and are used for the manufacturing material of other Industrial materials and Electrical and Electronic equipment, trolley part, office appliance, and house articles for use.
Embodiment
Specify by the following examples the present invention, but the present invention is not subjected to any restriction of these embodiment.Various characteristics in embodiment and the comparative example is all measured by the following method.
(1) carboxyl end group concentration:
Accurately take by weighing 0.5-2.0g polymeric amide sample, and be dissolved in being in the phenylcarbinol under 95 ℃ of 20ml.In resulting solution, add indicator-phenolphthalein, then use the titration of 0.02N KOH ethanolic soln.
(2) amino end group concentration:
Accurately take by weighing 0.5-2.0g polymeric amide sample, and solution 25ml be in phenol/ethanol (84: 16wt%) in the mixing solutions under the room temperature.In resulting solution, add indicator-thymolsulfonphthalein, then use 0.02N HCl titration.
(3) thermal property:
Adopt fusing point and the second-order transition temperature of Shimazu DSC-Q100 analytical instrument specimen, accurately take by weighing approximately the sample of 5mg and measure its fusing point and second-order transition temperature with the heating rate of 20 ℃/min.
(4) sulfuric acid relative viscosity:
Measuring concentration in 25 ℃ the vitriol oil is the relative viscosity of 0.1g/ml polymeric amide.
(5) 25 ℃ of saturated rate of moisture absorption
By hot pressing under the temperature higher 20 ℃ than fusing point and in frozen water, cool off, be the film sample of 0.2mm (50mm*50mm) from polymeric amide sample preparation thickness.Sample is dried to constant weight at 120 ℃, and weighing is immersed in 25 ℃ the water to constant weight again weighing.The weight ratio (%) that calculated weight increases and submergence is front.
(6) physical and mechanical properties:
The biomass-based polymeric amide injection moulding that contains of preparation is become the dumb-bell shape batten, (ISO 527 according to its tensile strength of standard testing of ISO and tensile elongation, three groups of data mean values), (ISO 178 for flexural strength, three groups of data mean values) and notched Izod impact strength (179, three groups of data mean values of ISO).
(7) biological substance ratio
Biological substance is than (%)=100 * from the weight of raw materials of the weight of the raw material of biological substance/all.
Be called for short explanation: TA: terephthalic acid, FCDA: furans-2,5 dioctyl phthalate, 3,4-FCDA:3,4-furans-3,4 dioctyl phthalate DA10:1,10-decamethylene diamine, DA6: hexanediamine, 5-HIA:5-Hydroxy M Phthalic Acid, DA8:1,8-octamethylenediamine, DA20:1,20-two amino dodecanes, DA4:1, the 4-butanediamine.
FCDA: purity is 98%, available from upper Hisoon specialization industry science skill company limited
TA: purity is 98%, available from Sigma-Aldrich company
DA10: purity is 98%, available from Wuxi company of Xingda
DA6: purity is 98%, available from Sigma-Aldrich company
5-HIA: purity is 98%, available from Sigma-Aldrich company
DA8: purity is 98%, available from Wuxi company of Xingda
DA20: purity is 98%, available from Sigma-Aldrich company
The sodium hypophosphite monohydrate: analytical pure, available from Sigma-Aldrich company
Phenylformic acid: analytical pure is available from Sigma-Aldrich company
DA4: purity is 98%, available from Sigma-Aldrich company
Embodiment 1
In the 3L autoclave, add 592.8g (3.8mol) furans-2,5-dioctyl phthalate, 33.2g (0.2mol) terephthalic acid, 688g (4mol) 1,10-decamethylene diamine, 2.62 (0.12mol) phenylformic acid, 2.62g (based on the 0.2wt% of raw material total amount) sodium hypophosphite monohydrate, 0.5L deionized water heats up behind the nitrogen purging.Under agitation with approximately being warming up to 215 ℃ in 2 hours, this moment, the pressure of autoclave inside rose to 2MPa.With this condition sustained reaction 2 hours, then be warming up to 240 ℃, under this condition, kept 2 hours, slowly go out water vapour, make pressure remain on 2MPa and react.Then, with 1 hour with Pressure Drop to 1MPa, further reacted 1 hour, obtain relative viscosity and be 1.6 prepolymer.
With the gained prepolymer 80 ℃ of drying under reduced pressure 20 hours, be ground into the following particle diameter of 2mm, under 230 ℃, 20Pa, carry out 10 hours solid state polymerization, obtain fusing point and be 295 ℃, sulfuric acid relative viscosity and be 2.6, the terminal amino group amount is that 45eq/ton, terminal carboxyl(group) amount are the white polyamide resin of 35eq/ton.Its mechanical property such as table one.
Embodiment 2
Repeat embodiment 1, different is furans-2, and the mol ratio of 5-dioctyl phthalate and terephthalic acid is to the results are shown in table one at 75: 25..
Embodiment 3
Repeat embodiment 1, different is furans-2, and the mol ratio of 5-dioctyl phthalate and terephthalic acid is to the results are shown in table one at 50: 50.
Embodiment 4
Repeat embodiment 1, different is that (c) is DA10, (d) is DA8, and its mol ratio is 90/10 to the results are shown in table one.
Embodiment 5
Repeat embodiment 1, different is that (c) is DA10, (d) is DA20, and its mol ratio is 90/10 to the results are shown in table one.
Embodiment 6
Repeat embodiment 1, different is that (c) is DA10, (d) is DA20, and its mol ratio is 72/28 to the results are shown in table one.
Embodiment 7
Repeat embodiment 1, different is that (a) is 3,4-FCDA, and the mol ratio of 3,4-FCDA and TA the results are shown in table one at 75: 25.
Comparative example 1
Repeat embodiment 1, different is not have (b) terephthalic acid units.The results are shown in table two.
Comparative example 2
Repeat embodiment 1, different is furans-2, and the mol ratio of 5-dioctyl phthalate and terephthalic acid is 35: 65.The results are shown in table two.
Comparative example 3
Repeat embodiment 1, different is furans-2, and the mol ratio of 5-dioctyl phthalate and terephthalic acid is 75: 25, and aliphatie diamine is DA4.The results are shown in table two.
Comparative example 4
Repeat embodiment 1, different is furans-2, and the mol ratio of 5-dioctyl phthalate and terephthalic acid and 5-Hydroxy M Phthalic Acid is 70: 5: 25, and aliphatie diamine is DA6.The results are shown in table two.
Comparative example 5
Repeat embodiment 1, different is furans-2, and the mol ratio of 5-dioctyl phthalate and terephthalic acid is 90: 10, and the mol ratio of aliphatie diamine DA10/DA20 is 60: 40.The results are shown in table two.
Table one embodiment
Table two comparative example
Claims (10)
1. one kind contains biomass-based polyamide resin, it is characterized in that: this contains biomass-based polyamide resin and contains:
(a) furans diprotic acid unit,
(b) terephthalic acid units,
(c) biomass-based 1，10-diaminodecane unit,
(d) (c) carbonatoms beyond the unit is binary aliphatic amine unit more than 4;
Wherein (a) unit content is (a) unit and (b) 50mol%～98mol% of the total amount of unit, and (d) unit content be (c) unit and (d) 0mol%～30mol% of the total amount of unit.
2. contain biomass-based polyamide resin as claim 1 is described, it is characterized in that: (a) furans diprotic acid unit is the furans diprotic acid unit of bio-based monomer.
3. contain biomass-based polyamide resin as claim 2 is described, it is characterized in that: (a) the furans diprotic acid unit of bio-based monomer is selected from furans-2,5 dioctyl phthalate, 3,4-dimethoxy furans-2, in 5-dioctyl phthalate or furans-3,4 dioctyl phthalate one or more.
4. contain biomass-based polyamide resin as claim 3 is described, it is characterized in that: (a) the furans diprotic acid unit of bio-based monomer is furans-2,5 dioctyl phthalate.
5. contain biomass-based polyamide resin as claim 1 is described, it is characterized in that: (d) carbonatoms beyond (c) unit is that to be selected from carbonatoms be in 4～18 the aliphatic diamine one or more for binary aliphatic amine unit more than 4.
6. contain biomass-based polyamide resin as claim 5 is described, it is characterized in that: carbonatoms is that 4～18 straight chain diamine is selected from 1, the 4-butanediamine, 1, the 5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octane diamines, 1, the 9-nonane diamine, 1,11-undecane diamines, 1,12-dodecane diamines, 1,13-tridecane diamines, 1,14-tetradecane diamines, 1,15-pentadecane diamines, 1,16-n-Hexadecane diamines, 1,17-heptadecane diamines, 1, the 18-octadecamethylene diamine, the 2-methyl isophthalic acid, 8-octane diamines, or the 5-methyl isophthalic acid, one or more in the 9-nonane diamine.
7. contain biomass-based polyamide resin as claim 1 is described, it is characterized in that: (d) unit content is (c) unit and (d) 0mol%～25mol% of the total amount of unit.
8. as each describedly contains biomass-based polyamide resin in the claim 1～7, it is characterized in that: described to contain biomass-based polyamide resin fusing point be 220 ℃～290 ℃.
9. as each describedly contains biomass-based polyamide resin in the claim 1～7, it is characterized in that: the described second-order transition temperature that contains biomass-based polyamide resin is 80 ℃～110 ℃.
10. as each describedly contains biomass-based polyamide resin in the claim 8, it is characterized in that: described 25 ℃ of saturated water absorptions that contain biomass-based polyamide resin are 4.0%～7.0%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059292A (en) * | 2013-02-05 | 2013-04-24 | 苏州瀚海化学有限公司 | Water-soluble copolyamide and preparation method thereof |
| CN103113577A (en) * | 2013-02-05 | 2013-05-22 | 苏州瀚海化学有限公司 | Alcohol-soluble copolyamide and preparation method thereof |
| WO2015059047A1 (en) | 2013-10-21 | 2015-04-30 | Solvay Specialty Polymers Usa, Llc | Polyamides containing the bio-based 2,5-furandicarboxylic acid |
| CN106884215A (en) * | 2017-02-24 | 2017-06-23 | 上海凯赛生物技术研发中心有限公司 | A kind of fluffy polyamide 5X Blulked continuous Filaments of flame-retardant flexible and its preparation method and application |
| CN108129657A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of synthetic method of biomass-based polyamide |
| CN110770278A (en) * | 2017-06-14 | 2020-02-07 | 索尔维特殊聚合物美国有限责任公司 | Copolyamides obtainable from 3- (aminomethyl) benzoic acid |
| KR20200083797A (en) * | 2018-12-28 | 2020-07-09 | 인하대학교 산학협력단 | Polyamide-imide copolymers and transparent films using the same |
| WO2023045820A1 (en) * | 2021-09-24 | 2023-03-30 | 珠海万通特种工程塑料有限公司 | Furan diacid-based polyamide, preparation method therefor, and furan diacid-based polyamide composition |
| WO2023045819A1 (en) * | 2021-09-24 | 2023-03-30 | 珠海万通特种工程塑料有限公司 | Furan diacid-based polyamide resin, preparation method therefor, and polyamide molding composition |
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- 2011-07-01 CN CN 201110195434 patent/CN102850541A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059292B (en) * | 2013-02-05 | 2015-08-26 | 苏州瀚海化学有限公司 | Water-soluble copolyamides and preparation method thereof |
| CN103113577A (en) * | 2013-02-05 | 2013-05-22 | 苏州瀚海化学有限公司 | Alcohol-soluble copolyamide and preparation method thereof |
| CN103059292A (en) * | 2013-02-05 | 2013-04-24 | 苏州瀚海化学有限公司 | Water-soluble copolyamide and preparation method thereof |
| CN103113577B (en) * | 2013-02-05 | 2015-05-20 | 苏州瀚海化学有限公司 | Alcohol-soluble copolyamide and preparation method thereof |
| US9951181B2 (en) | 2013-10-21 | 2018-04-24 | Synvina C.V. | Polyamides containing the bio-based 2,5-furandicarboxylic acid |
| WO2015059047A1 (en) | 2013-10-21 | 2015-04-30 | Solvay Specialty Polymers Usa, Llc | Polyamides containing the bio-based 2,5-furandicarboxylic acid |
| CN108129657A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of synthetic method of biomass-based polyamide |
| CN106884215A (en) * | 2017-02-24 | 2017-06-23 | 上海凯赛生物技术研发中心有限公司 | A kind of fluffy polyamide 5X Blulked continuous Filaments of flame-retardant flexible and its preparation method and application |
| CN106884215B (en) * | 2017-02-24 | 2020-06-05 | 上海凯赛生物技术股份有限公司 | Flame-retardant soft fluffy polyamide 5X continuous bulked filament and preparation method and application thereof |
| CN110770278A (en) * | 2017-06-14 | 2020-02-07 | 索尔维特殊聚合物美国有限责任公司 | Copolyamides obtainable from 3- (aminomethyl) benzoic acid |
| CN110770278B (en) * | 2017-06-14 | 2023-02-17 | 索尔维特殊聚合物美国有限责任公司 | Copolyamides obtainable from 3- (aminomethyl) benzoic acid |
| KR20200083797A (en) * | 2018-12-28 | 2020-07-09 | 인하대학교 산학협력단 | Polyamide-imide copolymers and transparent films using the same |
| KR102158816B1 (en) | 2018-12-28 | 2020-09-23 | 인하대학교 산학협력단 | Polyamide-imide copolymers and transparent films using the same |
| WO2023045820A1 (en) * | 2021-09-24 | 2023-03-30 | 珠海万通特种工程塑料有限公司 | Furan diacid-based polyamide, preparation method therefor, and furan diacid-based polyamide composition |
| WO2023045819A1 (en) * | 2021-09-24 | 2023-03-30 | 珠海万通特种工程塑料有限公司 | Furan diacid-based polyamide resin, preparation method therefor, and polyamide molding composition |
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