CN104098765A - Synthesis method for biologically based transparent semi-aromatic poly-amide material - Google Patents
Synthesis method for biologically based transparent semi-aromatic poly-amide material Download PDFInfo
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Abstract
The invention relates to a synthesis method for a biologically based transparent semi-aromatic poly-amide material, and belongs to the field of polyamide synthesis. The synthesis method is characterized by comprising the following steps: purifying a biologically based lignose material and performing acetylation treatment; conducting reaction for acetylated lignose material, aromatic dicarboxylic acid, aliphatic diamine of 6-12 carbon atoms in an organic solvent to prepare high purity salt; placing the salt obtained through the reaction, deionized water and polymeric additives into a high pressure reaction kettle, and performing prepolymerization under the condition of high-purity inert gas; after the prepolymerization, increasing temperature and pressure to further performing a polymerization reaction to obtain the novel biologically based transparent semi-aromatic poly-amide material. The novel biologically based transparent semi-aromatic poly-amide material has excellent transparency, heat resistance, electric insulativity and aging resistance, is high in strength, non-toxic, odor free and corrosion resistant, and can be widely applied to automotive industry, medicine devices, optical instruments, measure instruments, food packages, physical goods and the like.
Description
Technical field
The present invention relates to a kind of synthetic field of novel transparent polymeric amide; especially the present invention relates to the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based; relate to specifically a kind of xylogen of processing by acetylize, fragrant di-carboxylic acid and aliphatic diamine; under the effect of reagent and additive in polymerization, a kind of novel bio-based semi-aromatic polyamide material synthesizing in reactor.
Background technology
Polymeric amide is commonly called as nylon (PA), refer to have on macromolecular chain the polymkeric substance of amide group (CONH-) repeated structural unit, since develop by the W.H Carothers of institute of du pont company central authorities from the thirties in 20th century and realizing suitability for industrialized production, had the history of more than 60 year.The production initial stage is mainly used in spinning, and early 1950s is just used as engineering plastics.Due to it, to have physical strength high, and impelling strength is good, the features such as thermotolerance, wear resistance and oil-proofness excellence, and the every field in national economy such as machinery, national defence, chemical industry, traffic and water conservancies obtains application widely.
It is excellent that transparent polyamide has the transparency, thermally-stabilised, dimensional stability, electrical insulating property and ageing resistance, intensity is high, nontoxic, odorless, molding shrinkage is low, linear expansivity is little, corrosion-resistant, easily, with the feature such as other amorphous or hemihedral crystal polymeric amide formation alloy, can be used for the aspects such as automotive industry, opticinstrument, precise part, measuring instrument, food product pack and high-grade sports equipment and be widely used.
Along with the enhancing of human environment protection consciousness, biological plastics is shown great attention to by the scientific research personnel of countries in the world.Especially in the past in 5 years, take biology as basic material is by more show-and-tell, the high biological plasticss of cost performance such as poly(lactic acid) (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), poly butylene succinate (PBS) have been pushed to the market, in fields such as food product pack, container, electronic product components, are widely used.Biological poly acid amides is at present according to internationally recognized definition, and wherein PA11, PA1010 are safe biologic based polyamide, and PA610, PA1012, PA410, PA10T are part biological based polyamide, other be petrochemical industry base kind.Although biological poly acid amides can't be degradable, its range of application is compared also narrow with general-purpose plastics, but it greatly reduces the impact of petrochemical industry based polyamide to environment, therefore its development polymeric amide is also subject to the impact of factor in evolution, such as manufacturing cost is higher, the finiteness of renewable proportion of crop planting and with the competition of food, affect the risk of diversity of organism etc.But generally speaking, the gradually minimizing of the public to the attention rate of environment and petrochemical industry base resource, developing biological polymeric amide is a kind of inevitable trend.
In state key program for tackling key problems in science and technology is listed the new renewable resources petroleum replacing of exploitation by China.In < < national science technology Long-and Medium-term Development planning outline > >, point out " new material technology is by the compoundization of structure function to material, use procedure greenization development ".In the high-technology field that state key is supported, clearly propose " take reproducible biomass prepare macromolecular material for starting material ".In " 12 " in country and many areas planning, all mention the extension of biological industry chain, to promote biological industry, enter national economy systemic circulation.
At present, domestic transparent polyamide Year's consumption has reached more than 2000 tons, but due to the aliphatic diamine for the synthesis of transparent polyamide and the domestic not yet suitability for industrialized production of dicarboxylic acid monomer, so do not succeed in developing so far transparent polyamide, needed product all need to be from external import, price is up to more than 30,000 yuan/ton, in order to meet the needs to transparent polyamide both at home and abroad, solve the problem of the long-term dependence on import of transparent polyamide, so the research of bio-based transparent polyamide has very important realistic meaning.
Summary of the invention
The object of the present invention is to provide a kind of bio-based xylogen of having introduced is synthesis material, greatly reduce synthetic cost, the transparent polyamide that uses this method to prepare, there is good moulding processability, transmittance is high, fusing point is high, mechanical property is high, improved synthesis technique, has expanded the synthetic method of the use of transparent polyamide product and the transparent semi-aromatic polyamide material of the bio-based of range of application.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is that the transparent semi-aromatic polyamide material of a kind of bio-based and synthetic method thereof, mainly comprise the following steps:
(1) first bio-based lignin material being carried out to purifying acetylize processes: xylogen is placed in to toluene/ethanol (volume ratio=1:2) solution normal temperature and pressure and stirs 3-12 hour, then filter, ethanolic soln with 95% cleans 1-3 time, obtains purer xylogen; Purifying xylogen and diacetyl oxide are placed in to glacial acetic acid according to the ratio of mol ratio 1:2, and adding the vitriol oil (0.5-1wt%) is catalyzer, under the condition refluxing, reacts 4-12 hour, after having reacted, filters, dry, obtains acetylizad xylogen;
(2) acetylizad xylogen, aromatic binary carboxylic acid, a 6-12 fat of carbon atom family diamine, organic solvent are placed in to reactor, in stirring, temperature, be under 60 ℃ of-130 ℃ of conditions, reaction 1-6 hour, when PH is 6.5-8, coolingly obtains highly purified amide salt;
(3) salt then above-mentioned reaction being made, deionized water and reagent and additive in polymerization are placed in reactor, in temperature, it is 200 ℃-310 ℃, reaction times is 1-5 hour, is full of under the condition of high purity inert gas normal pressure and carries out prepolymerization, makes low-molecular-weight polyamide prepolymer polymers;
(4) then improve temperature to 250 ℃-350 ℃, pressure is 1-5MPa, and the time is 1-6 hour, after reacting completely, then in 0.5-3 hour, be decompressed to normal pressure, then react discharging in 0.5-3 hour, cooling, pelletizing makes the transparent semi-aromatic polyamide material of bio-based.
The bio-based xylogen of above-mentioned steps (1) is the xylogen through special purifying acetylize processing, and acetylation reagent is wherein one or both in MALEIC ANHYDRIDE or terephthalic anhydride, preferably terephthalic anhydride.
Aromatic binary carboxylic acid in above-mentioned steps (2) is one or both in terephthalic acid or m-phthalic acid, preferably terephthalic acid.
Diamine in above-mentioned steps (2) is 1,6-hexanediamine, 1, one or more in the amino undecane of 9-nonamethylene diamine, 1，10-diaminodecane and 1,11-, preferred 1，10-diaminodecane, 1, the amino undecane of 11-.
Organic solvent in above-mentioned steps (2) is one or both in N-Methyl pyrrolidone or dimethyl formamide, preferably dimethyl formamide.
In above-mentioned steps (2), mole proportioning of each component is: acetylizad xylogen: aromatic binary carboxylic acid: aliphatic diamine=1: 1: 2.
Catalyzer in above-mentioned steps (3) is one or more in phosphoric acid, phosphorous acid or hypophosphite, and preferably Hypophosporous Acid, 50 is received.
Rare gas element in above-mentioned steps (3) is one or more in carbonic acid gas, nitrogen or argon gas, preferred nitrogen.
In above-mentioned steps (3), the quality proportioning of each component is (wt%):
Prepared salt: 99.45-94 in step (2);
Catalyzer: 0.05-1;
End-capping reagent: 0.5-5.
The transparent semi-aromatic polyamide of bio-based that method of the present invention is produced, except transparent excellence, also has good thermostability, and dimensional stability etc., have a wide range of applications in fields such as opticinstrument, precise part and high-grade sports equipments.Transmittance is greater than 90%, technology maturation, and the synthesis material of its polymerization single polymerization monomer derives from xylogen, and wherein xylogen is extensively present in each kind of plant, and in the Nature, reserves are abundant, have very high environmental protection and economical and practical value.
Embodiment
Technical characterstic for a better understanding of the present invention, below in conjunction with the present invention is further illustrated by embodiment, it should be noted that, the present embodiment is not limiting the scope of the invention.
Embodiment 1
The mixing solutions that 1Kg xylogen is placed in to the toluene/ethanol (volume ratio=1:2) of 7L, stirs 6h at normal temperatures and pressures, then filters, and the ethanolic soln with 95% cleans 2-3 time, dry, obtains purer xylogen.The terephthalic anhydride of the xylogen of purifying 0.5mol purifying and 1mol is placed in to the glacial acetic acid of 7L according to the ratio of mol ratio 1:2; adding the vitriol oil (0.5-1wt%) is catalyzer, under the condition refluxing, reacts 8h, after having reacted, filters; dry, obtain acetylizad xylogen.
Take the above-mentioned acetylizad xylogen of 2mol, 2mol terephthalic acid, 4mol1; 10-decamethylene diamine is placed in the dimethyl formamide organic solvent of 15L, at 105 ℃, reacts 5 hours under the condition of stirring; cooling after reacting completely, filtration, obtain purer amide salt.
The amide salt 2mol of above-mentioned preparation, deionized water 50mol, phenylformic acid (0.6mol), hypochlorous acid are received to (0.08mol) in reactor, temperature controls 230 ℃, under the atmosphere of high pure nitrogen, stirring reaction 3 hours, after reacting completely, then promote temperature to 260 ℃, boost in pressure, to 3MPa, is reacted 3 hours, after reacting completely, then in 1 hour, be decompressed to normal pressure, then react discharging in 1 hour, cooling, pelletizing makes the transparent semi-aromatic polyamide material of bio-based.
Embodiment 2
By the method that embodiment 1 is same, xylogen is carried out to acetylize processing.
Take the above-mentioned acetylizad xylogen of 2mol, 2mol terephthalic acid, 4mol1; the amino undecane of 11-is placed in the dimethyl formamide organic solvent of 15L, at 105 ℃, reacts 5 hours under the condition of stirring; cooling after reacting completely, filtration, obtain purer amide salt.
The amide salt 2mol of above-mentioned preparation, deionized water 50mol, phenylformic acid (0.6mol), hypochlorous acid are received to (0.08mol) in reactor, temperature controls 230 ℃, under the atmosphere of high pure nitrogen, stirring reaction 3 hours, after reacting completely, then promote temperature to 260 ℃, boost in pressure, to 3MPa, is reacted 3 hours, after reacting completely, then in 1 hour, be decompressed to normal pressure, then react discharging in 1 hour, cooling, pelletizing makes the transparent semi-aromatic polyamide material of bio-based.
Table 1 is the performance index of the transparent semi-aromatic polyamide material of the prepared bio-based of embodiment 1-2
In sum, be preferred embodiment of the present invention, all changes of having done according to technical solution of the present invention, when the function producing fails to exceed the scope of technical solution of the present invention, all belong to protection scope of the present invention.
Claims (9)
1. a synthetic method for the transparent semi-aromatic polyamide material of bio-based, is characterized in that following steps:
(1) first bio-based lignin material being carried out to purifying acetylize processes: xylogen is placed in to toluene/ethanol (volume ratio=1:2) solution normal temperature and pressure and stirs 3-12 hour, then filter, ethanolic soln with 95% cleans 1-3 time, obtains purer xylogen; Purifying xylogen and diacetyl oxide are placed in to glacial acetic acid according to the ratio of mol ratio 1:2, and adding the vitriol oil (0.5-1wt%) is catalyzer, under the condition refluxing, reacts 4-12 hour, after having reacted, filters, dry, obtains acetylizad xylogen;
(2) acetylizad xylogen, aromatic binary carboxylic acid, a 6-12 fat of carbon atom family diamine, organic solvent are placed in to reactor, in stirring, temperature, be under 60 ℃ of-130 ℃ of conditions, reaction 1-6 hour, when PH is 6.5-8, coolingly obtains highly purified amide salt;
(3) salt then above-mentioned reaction being made, deionized water and reagent and additive in polymerization are placed in reactor, in temperature, it is 200 ℃-310 ℃, reaction times is 1-5 hour, is full of under the condition of high purity inert gas normal pressure and carries out prepolymerization, makes low-molecular-weight polyamide prepolymer polymers;
(4) then improve temperature to 250 ℃-350 ℃, pressure is 1-5MPa, and the time is 1-6 hour, after reacting completely, then in 0.5-3 hour, be decompressed to normal pressure, then react discharging in 0.5-3 hour, cooling, pelletizing makes the transparent semi-aromatic polyamide material of bio-based.
2. the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based according to claim 1; it is characterized in that described bio-based xylogen is for the xylogen through special purifying acetylize processing, acetylation reagent is wherein one or both in MALEIC ANHYDRIDE or terephthalic anhydride.
3. the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based according to claim 1, is characterized in that described aromatic binary carboxylic acid is one or both in terephthalic acid or m-phthalic acid.
4. the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based according to claim 1, is characterized in that described diamine is 1,6-hexanediamine, 1, one or more in the amino undecane of 9-nonamethylene diamine, 1，10-diaminodecane and 1,11-.
5. the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based according to claim 1, its feature is one or both in N-Methyl pyrrolidone or dimethyl formamide at described organic solvent.
6. according to the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based claim 1 step (2) Suo Shu, it is characterized in that mole proportioning of described each component is: acetylizad xylogen: aromatic binary carboxylic acid: aliphatic diamine=1: 1: 2.
7. the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based according to claim 1, it is characterized in that described reagent and additive in polymerization comprises catalyzer, end-capping reagent, wherein catalyzer is one or more in phosphoric acid, phosphorous acid or hypophosphite, and end-capping reagent is one or more in phenylformic acid, toluylic acid, aniline or para-totuidine.
8. the synthetic method of the transparent semi-aromatic polyamide material of a kind of bio-based according to claim 1, is characterized in that described rare gas element is one or more in carbonic acid gas, nitrogen or argon gas.
9. according to the transparent semi-aromatic polyamide material of a kind of bio-based and synthetic method thereof claim 1 step (3) Suo Shu, the quality proportioning that it is characterized in that described each component is (wt%):
Prepared salt: 99.45-94 in step (2);
Catalyzer: 0.05-1;
End-capping reagent: 0.5-5.
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| CN111925521A (en) * | 2019-05-13 | 2020-11-13 | 中国石油天然气股份有限公司 | Full-bio-based polyamide and preparation method thereof |
| CN112300384A (en) * | 2020-09-18 | 2021-02-02 | 北京绿程生物材料技术有限公司 | Bio-based nylon, modified material thereof, preparation method and application of 3D printing |
| CN113683900A (en) * | 2021-08-25 | 2021-11-23 | 南京工业大学 | Modified lignin-polyamide-based thermosetting composite material and preparation method thereof |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
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Cited By (4)
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