CN104193989A - Preparation method of bio-based polyamide copolymer elastomer - Google Patents
Preparation method of bio-based polyamide copolymer elastomer Download PDFInfo
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Abstract
The invention relates to a preparation method of a bio-based polyamide copolymer elastomer and belongs to the field of macromolecular materials. The preparation method of the bio-based polyamide copolymer elastomer comprises the following steps: 1) preparing itaconic acid, sebacic acid, decamethylene diamine and butanediamine bio-based polyamide, and drying the obtained bio-based polyamide at the temperature of 40-50 DEG C for 24-48 hours under vacuum condition; 2) carrying out vacuum tabletting and moulding, placing fully dried bio-based polyamide into a mould of a vacuum tabletting machine, and tabletting at the temperature of 160-180 DEG C under vacuum condition, so that a bio-based polyamide panel with the thickness of 1-4mm is obtained; 3) cutting the bio-based polyamide panel into various samples by virtue of a pneumatic cutting machine; and 4) preparing an elastomer, namely soaking the bio-based polyamide panel samples in deionized water for modifying for 24-96 hours, so that the polyamide elastomer is obtained. The bio-based polyamide copolymer elastomer obtained by adopting the preparation method provided by the invention has good processability, cytotoxicity and environmental stability, does not pollute the environment and is degradable.
Description
Technical field
The present invention relates to a kind of method of modifying of fatty polyamide multipolymer, particularly a kind of biological poly acid amides based on renewable resources and the method for modifying of green non-pollution, belong to polymeric material field.
Background technology
Current, the non-renewable fossil energies such as the coal that the mankind use, oil and natural gas are about to face exhausted problem (oil can be used 40 years, coal can use 200 years, Sweet natural gas can use 60 years).Moreover be accompanied by the consumption of fossil energy, global climate changes and the also serious life of perplexing people of the problem such as environmental pollution.So many countries are using Renewable Energy Development as the important measures of alleviating energy supply and demand contradiction, reply climate change.Biomass as at present in the world most widely used renewable energy source be unique charcoal capable of circulation, reproducible source, total quantity consumed occupies the 4th, the world, its Efficient Conversion and clean utilization more and more come into one's own.
Polymeric amide (PA) claim again nylon, refers to the linear thermoplastic's polymkeric substance that has amide group (CONH) repeated structural unit on main chain.Polyamide material is due to its excellent performance and be applied in widely in modern society life and played the part of very important role.Polymeric amide is normally made by diprotic acid and diamine or lactan or amino acid polycondensation, and principal item has PA6, PA66, PA1010, PA612, PA11, PA12 etc. at present.Aspect the research and development of biological poly acid amides, China has researched and developed 100% bio-based PA1010 voluntarily, and this material has become one of important engineering plastics kind of China at present; France Arkema company has released 100% bio-based PA11 engineering plastics; Germany Evonik company has also successfully developed the polymeric amide product such as 45% bio-based PA1012,62% bio-based PA610 in recent years; 2009, Dutch DSM N. V. released the PA410 engineering plastics of 70% bio-based; 2010, German Basf company and French Rhodia company all released the PA610 polyamide article of part biological base.
Polymeric amide is because the amide group polarity in molecular structure is high, intermolecular easy formation hydrogen bond, so polymeric amide has wear-resisting, shock-resistant, antifatigue, corrosion-resistant, oil resistant, resistance to solvent, the good characteristic such as nontoxic.For adapting to the particular requirement in different application field, polymeric amide is carried out modification conventionally, the modification technologies such as conventional block, graft-blending, filling and technique are developed in succession, have developed the polymeric amide novel material of toughness reinforcing, enhancing and plasticising, have further promoted the application of Polyamide Engineering Plastic.
Polymeric amide type elastomerics is to introduce soft chain segment structure in traditional polymeric amide molecular structure at present, and modal soft chain segment structure is polyethers or polyester.Normally in polymeric amide building-up process, add end carboxyl or hydroxyl telechelic polyester and polyether-type monomer copolymerization.In existing biological poly acid amides except PA1010 and PA11, other are all the polymkeric substance of part biological base, and these biological poly acid amides are often used as engineering plastic materials at present, rarely has the reported in literature using as elastomerics about 100% biological poly acid amides self.Therefore, carry out the elastomeric research of biological poly acid amides and there is great application prospect, simultaneously also to promoting the Application Areas of expansion polyamide material significant.
Summary of the invention
The object of this invention is to provide a kind of biological poly amide copolymer method for producing elastomers.Employing obtains biomass monomer methylene-succinic acid, sebacic acid, butanediamine and decamethylene diamine melt phase polycondensation by bio-based extraction and obtains biological poly acid amides, by regulating the ratio of methylene-succinic acid and sebacic acid, when methylene-succinic acid content account for mixed dibasic acid total moles monomer (mole dosage of methylene-succinic acid and sebacic acid and) 60% and when above this biological poly acid amides embody a kind of transparent undefined structure, its second-order transition temperature is at 40-58 ℃, and viscosity-average molecular weight is 40854～62308.Our resulting biological poly acid amides is because a large amount of amino groups first makes it into ring with the two key generation addition reactions on methylene-succinic acid monomer side group, causes amide group (CONH) thereby this biological poly acid amides of the density of repeating structure decline recrystallize not.The polyamide material of current unformed class still rarely has report.
It is carried out after water plasticising, because water molecules is inserted between polymer molecular chain, has further weakened the reactive force of polymer molecule interchain, result increased polymer molecular chain movability, flexibility, flexibility, the plasticity of polymkeric substance is increased; Reduced the crystallizing power between modulus, second-order transition temperature, softening temperature and the molecular chain of polymkeric substance, and on water molecules-OH group easily reacts with remaining on polymer molecular chain-NH-group generation hydrogen bond the Intermolecular Forces that has further weakened polymkeric substance.Thereby changing rubbery state into the biological poly acid amides that originally presents plastics form after water molecules plasticising.
The most outstanding is when methylene-succinic acid content account for mixed dibasic acid total moles monomer (mole dosage of methylene-succinic acid and sebacic acid with) 80% time, the water-intake rate of this polymeric amide only 24h can reach 11%, the highlyest can reach 25%.Far away higher than the water-intake rate of traditional polyamide material, the water content saturation value of PA6 is 9.5%, the saturation value of PA66 is 8.5%, remaining is if PA11, PA46, PA610 etc. are all in 3.0% left and right (related data is published from < < Polymer Data Handbook > > for 1999).This transparent nontoxic polyamide elastomer material can have wide prospect of the application as aspects such as contact lens at water-absorbing resin.
A kind of biological poly acid amides method for producing elastomers provided by the present invention, concrete steps and reaction conditions are:
1, the preparation of biological poly acid amides
Employing derives from reproducible Biological resources methylene-succinic acid, sebacic acid, decamethylene diamine and butanediamine monomer and carries out melt polycondensation reaction, produces biological poly acid amides.Synthetic reaction formula is as follows:
In formula: a is any positive integer, it is the sum of clothing health acyl butanediamine chain link;
B is any positive integer, is the sum of sebacoyl butanediamine chain link;
C is any positive integer, is the sum of clothing health acyl decamethylene diamine chain link;
D is any positive integer, is the sum of sebacoyl decamethylene diamine chain link;
The order arbitrary arrangement of above-mentioned four kinds of segments or chain link wherein.
When methylene-succinic acid content account for mixed dibasic acid total moles monomer 100% time, building-up reactions formula is as follows:
In formula: a is any positive integer, it is the sum of clothing health acyl butanediamine chain link;
B is any positive integer, is the sum of clothing health acyl decamethylene diamine chain link.
1) monomer dissolving, salify
Methylene-succinic acid and sebacic acid are joined in dehydrated alcohol, be heated to 65 ℃ and make it to dissolve completely.Butanediamine and decamethylene diamine are joined in dehydrated alcohol, be heated to 50 ℃ and make it to dissolve completely.The ethanolic soln of above-mentioned hybrid diamine monomer is poured in the ethanolic soln of above-mentioned mixing diacid monomer, at 50 ℃, continue to stir 10-12min, after crystallisation by cooling, suction filtration, obtain crystal, with absolute ethanol washing gained crystal 3～5 times, then proceeded to and in culture dish, put into the vacuum drying oven of 30 ℃ and be dried 12 hours, obtained amide salt.
Wherein, mixed dibasic acid monomer is 1:1 with total mol ratio of mixing diamine monomer.Methylene-succinic acid accounts for mixed dibasic acid total moles monomer, the mole dosage of methylene-succinic acid and sebacic acid and 70%～100%, butanediamine accounts for and mixes diamine total moles monomer, the mole dosage of decamethylene diamine and butanediamine and 50%.
2) melt phase polycondensation
Above-mentioned amide salt is joined in the there-necked flask that mechanical stirring, thermometer are housed together with stablizer, vacuumize oxygen is removed completely; Under nitrogen protection, be heated to 180 ℃, keep this temperature within 1 hour, to make the complete melting of material; Continue to be warming up to 200 ℃ of reactions 2～4 hours, obtain polymkeric substance mucus; Then continue to be warming up to 210 ℃, close nitrogen, be evacuated to 0.01atm, then react and after 2-8 hour, stop heating, keep vacuum until reactor cooling; After cooled polymkeric substance mucus is pulverized, filtered, then boil, filter with ethanol, repeat 3～5 times, finally in vacuum drying oven, dry, obtain biological poly amide copolymer.
Demonomerization proportioning difference causes beyond polymerization mechanism difference, and above content is the patent of Beijing University of Chemical Technology's application: a kind of biological poly amide copolymer and synthetic method thereof; Application number is: 201210566786.4, and the applying date is on December 23rd, 2012; So be not re-used as claim.Provide now just insufficient for fear of disclosing.
The present invention selects monomer mole ratio (sebacic acid: methylene-succinic acid: decamethylene diamine: butanediamine) for 0:10:5:5,2:8:5:5 and 3:7:5:5 prepare biological poly acid amides.
2, the elastomeric preparation of biological poly acid amides
1) dry: by the biological poly acid amides making dry 24-48h under 40-50 ℃ of vacuum condition;
2) vacuum compression molding: fully dry biological poly acid amides is put into the mould of vacuum tabletting machine, carried out compressing tablet under the vacuum condition of 160～180 ℃, obtain biology and polymeric amide sheet material that thickness is 1～4mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is immersed in deionized water to 24～96h and material is carried out to plasticization and modification obtains bio-based polyamide elastomer, and measure its water-intake rate.
Adopt bio-based polyamide elastomer of the present invention to possess following characteristics: (1) raw materials does not rely on fossil resource, can prepare by reproducible Biological resources; (2) multipolymer that polymerization obtains is because methylene-succinic acid proportion in system is higher, and the polyamide material obtaining is a kind of transparent amorphous material; (3) method of modifying environmental protection used is not polluted; (4) polyamide elastomer making has good processing characteristics, cytotoxicity and environmental stability and environment is not polluted to degradable; (5) when methylene-succinic acid content reaches 80% the water-intake rate of polymeric amide only 24h can reach 11%, the highlyest can reach 25%, far away higher than the water-intake rate of traditional polyamide material.
Below in conjunction with embodiment, the invention will be further described.
Accompanying drawing explanation
Fig. 1 the present invention prepares biological poly amide copolymer reaction mechanism schematic diagram, can confirm by the nuclear magnetic spectrogram of Fig. 3.In formula: a is any positive integer, it is the sum of clothing health acyl butanediamine chain link; B is any positive integer, is the sum of sebacoyl butanediamine chain link; C is any positive integer, is the sum of clothing health acyl decamethylene diamine chain link; D is any positive integer, is the sum of sebacoyl decamethylene diamine chain link.The order arbitrary arrangement of above-mentioned four kinds of segments or chain link wherein.
Fig. 2 be when methylene-succinic acid content account for mixed dibasic acid total moles monomer 100% time reaction formula.In formula: a is any positive integer, it is the sum of clothing health acyl butanediamine chain link; B is any positive integer, is the sum of clothing health acyl decamethylene diamine chain link; The order arbitrary arrangement of above-mentioned two kinds of segments or chain link wherein.The 1H NMR nuclear magnetic spectrogram of the biological poly amide copolymer preparing in Fig. 3 embodiment of the present invention 4～7.
The extension recovery curve of Fig. 4 polyamide elastomer
The XRD curve of the bio-based polyamide material of the different methylene-succinic acid content of Fig. 5.
Fig. 3 is the 1H NMR nuclear magnetic spectrogram of the biological poly amide copolymer for preparing in the embodiment of the present invention 4～7.Can find out, all nucleus magnetic resonance bands of a spectrum of the biological poly acid amides of preparing by melt phase polycondensation are consistent with the molecular structure of design.When methylene-succinic acid content account for mixed dibasic acid total moles monomer 100% time, in figure, representative is positioned at the disappearance of the hydrogen characteristic peak a ' (7.72～7.86ppm) on imine group on straight chain, first having there is annulation with diamine polycondensation occurred again in the methylene-succinic acid that proves all participations reaction, reacts substantially complete.
Fig. 5 is the XRD curve of the bio-based polyamide material of different methylene-succinic acid content.As can be seen from the figure when methylene-succinic acid content is greater than 60% and when above, polyamide material changes to amorphous structure from crystal form.
Embodiment
The preparation of biological poly acid amides adopts the polymerization process of melt phase polycondensation, and melt phase polycondensation is three steps: the melting of ammonium salt, prepolymerization and post polymerization.In reactor in poly-unit (stainless steel agitator being housed, tri-mouthfuls of round-bottomed flasks of 500mL of nitrogen inlet and prolong), add the ammonium salt powder obtaining.With the light compacting reactant of glass stick, to prevent from vacuumizing subsequently ammonium salt powder in the process of leading to nitrogen, by air-flow, blown away subsequently.Before reactor heating, first system is evacuated to gauge outfit and shows negative pressure, keep 2min, pass into nitrogen subsequently until vacuum meter back to zero, at least 3 times so repeatedly, to guarantee existing of no oxygen in reactor.Start heating, all the time at N
2protection under the temperature of oil bath pan is warming up to 180 ℃, ammonium salt is melted 1 hour; Temperature is risen to 200 ℃ subsequently, react 2 hours.Afterwards, continue to be warming up to 210 ℃ of reactions after one hour, and close N
2, be evacuated to-0.01atm, react the source of reducing phlegm and internal heat of dropping back for 1 hour, keep vacuum, after question response device is cooling, stopped reaction.
Embodiment 1
1) dry: by biological poly acid amides dry 48h under 40 ℃ of vacuum conditions that the viscosity-average molecular weight making is 40854, monomer mole ratio is 3:7:5:5;
2) vacuum compression molding: fully dry biological poly acid amides 7.5g is put into the 10cm*10cm mould of vacuum tabletting machine, carry out compressing tablet under the vacuum condition of 160 ℃, obtaining thickness is the biological poly acid amides sheet material of 1mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is carried out obtaining bio-based polyamide elastomer after modification 24h to material with deionized water, resulting bio-based polyamide elastomer breaking tenacity is 4.5MPa, elongation at break is 300%, and its saturated water absorption in deionized water is 7.8%.This polyamide elastomer performance is in Table 1.
Embodiment 2
1) dry: by biological poly acid amides dry 48h under 45 ℃ of vacuum conditions that the viscosity-average molecular weight making is 40854, monomer mole ratio is 3:7:5:5;
2) vacuum compression molding: fully dry biological poly acid amides 7.5g is put into the 10cm*10cm mould of vacuum tabletting machine, carry out compressing tablet under the vacuum condition of 170 ℃, obtaining thickness is the biological poly acid amides sheet material of 2mm
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is carried out to modification 48h with deionized water to material and obtain bio-based polyamide elastomer, resulting bio-based polyamide elastomer breaking tenacity is 4.2MPa, elongation at break is 270%, and its saturated water absorption in deionized water is 11.3%.This polyamide elastomer performance is in Table 1.
Embodiment 3
1) dry: by biological poly acid amides dry 48h under 50 ℃ of vacuum conditions that the viscosity-average molecular weight making is 40854, monomer mole ratio is 3:7:5:5;
2) vacuum compression molding: fully dry biological poly acid amides 7.5g is put into the 10cm*10cm mould of vacuum tabletting machine, carry out compressing tablet under the vacuum condition of 180 ℃, obtaining thickness is the biological poly acid amides sheet material of 4mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is carried out to modification 96h with deionized water to material and obtain bio-based polyamide elastomer, resulting bio-based polyamide elastomer breaking tenacity is 3.7MPa, elongation at break is 230%, and its saturated water absorption in deionized water is 14.3%.This polyamide elastomer performance is in Table 1.
Embodiment 4
1) dry: by biological poly acid amides dry 48h under 40 ℃ of vacuum conditions that the viscosity-average molecular weight making is 55076, monomer mole ratio is 2:8:5:5;
2) vacuum compression molding: fully dry biological poly acid amides 7.5g is put into the 10cm*10cm mould of vacuum tabletting machine, carry out compressing tablet under the vacuum condition of 160 ℃, obtaining thickness is the biological poly acid amides sheet material of 1mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is carried out to modification 24h with deionized water to material and obtain bio-based polyamide elastomer, resulting bio-based polyamide elastomer breaking tenacity is 5.1MPa, elongation at break is 320%, and its saturated water absorption in deionized water is 11.0%.This polyamide elastomer performance is in Table 1.
Embodiment 5
1) dry: by biological poly acid amides dry 48h under 45 ℃ of vacuum conditions that the viscosity-average molecular weight making is 55076, monomer mole ratio is 2:8:5:5;
2) vacuum compression molding: fully dry biological poly acid amides 7.5g is put into the 10cm*10cm mould of vacuum tabletting machine, carry out compressing tablet under the vacuum condition of 170 ℃, obtaining thickness is the biological poly acid amides sheet material of 2mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is carried out to modification 48h with deionized water to material and obtain bio-based polyamide elastomer, resulting bio-based polyamide elastomer breaking tenacity is 4.7MPa, elongation at break is 280%, and its saturated water absorption in deionized water is 19.6%.This polyamide elastomer performance is in Table 1.
Embodiment 6
1) dry: by biological poly acid amides dry 48h under 50 ℃ of vacuum conditions that the viscosity-average molecular weight making is 55076, monomer mole ratio is 2:8:5:5;
2) vacuum compression molding: fully dry biological poly acid amides 7.5g is put into the 10cm*10cm mould of vacuum tabletting machine, carry out compressing tablet under the vacuum condition of 180 ℃, obtaining thickness is the biological poly acid amides sheet material of 4mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is carried out to modification 96h with deionized water to material and obtain bio-based polyamide elastomer, resulting bio-based polyamide elastomer breaking tenacity is 4.2MPa, elongation at break is 240%, its saturated water absorption in deionized water is 25.1%, and this sample is the material of over-all properties the best.This polyamide elastomer performance is in Table 1.
Embodiment 7
1) dry: by biological poly acid amides dry 48h under 50 ℃ of vacuum conditions that the viscosity-average molecular weight making is 62308, monomer mole ratio is 0:10:5:5;
2) vacuum compression molding: fully dry biological poly acid amides 7.5g is put into the 10cm*10cm mould of vacuum tabletting machine, carry out compressing tablet under the vacuum condition of 180 ℃, obtaining thickness is the biological poly acid amides sheet material of 4mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is carried out to modification 96h with deionized water to material and obtain bio-based polyamide elastomer, resulting bio-based polyamide elastomer breaking tenacity is 2.5MPa, elongation at break is 130%, because methylene-succinic acid content is 100%, amide group between molecular chain declines greatly, thereby micromolecular water very easily enters in polymkeric substance and causes mechanical property significantly to decline.This polyamide elastomer performance is in Table 1.
The polyamide elastomer performance table that table 1 prepares
Note: in table, the physical mechanical Mechanics Performance Testing standard of polymeric amide is GB/T 1040.
Claims (3)
1. a biological poly amide copolymer elastomerics, is characterized in that structural formula is as follows:
In formula: a is any positive integer, it is the sum of clothing health acyl butanediamine chain link;
B is any positive integer, is the sum of sebacoyl butanediamine chain link;
C is any positive integer, is the sum of clothing health acyl decamethylene diamine chain link;
D is any positive integer, is the sum of sebacoyl decamethylene diamine chain link;
The order arbitrary arrangement of above-mentioned four kinds of segments or chain link wherein, and viscosity-average molecular weight is 40854～62308;
When methylene-succinic acid content account for mixed dibasic acid total moles monomer 100% time, structural formula is as follows:
In formula: a is any positive integer, it is the sum of clothing health acyl butanediamine chain link;
B is any positive integer, is the sum of clothing health acyl decamethylene diamine chain link.
2. the preparation method of biological poly amide copolymer according to claim 1, is characterized in that:
1) raw material sebacic acid: methylene-succinic acid: decamethylene diamine: butanediamine monomer mole ratio is 3:7:5:5,2:8:5:5 and 0:10:5:5;
2) biological poly acid amides reaction formula is as follows:
In formula: a is any positive integer, it is the sum of clothing health acyl butanediamine chain link;
B is any positive integer, is the sum of sebacoyl butanediamine chain link;
C is any positive integer, is the sum of clothing health acyl butanediamine chain link;
D is any positive integer, is the sum of sebacoyl decamethylene diamine chain link;
The order arbitrary arrangement of above-mentioned four kinds of segments or chain link wherein.
When methylene-succinic acid content account for mixed dibasic acid total moles monomer 100% time, reaction formula is as follows:
3. the multipolymer that prepared by method according to claim 2 is prepared the elastomeric method of biological poly acid amides, it is characterized in that:
1) by the biological poly acid amides making dry 24-48h under 40-50 ℃ of vacuum condition;
2) vacuum compression molding: fully dry biological poly acid amides is put into the mould of vacuum tabletting machine, carried out compressing tablet under the vacuum condition of 160～180 ℃, obtaining thickness is the biological poly acid amides sheet material of 1～4mm;
3) cut out sample: biological poly acid amides sheet material is cut into various samples under pneumatic slitter;
4) prepare elastomerics: biological poly acid amides sample is immersed in deionized water to 24-96h and material is carried out to modification obtains bio-based polyamide elastomer.
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Application publication date: 20141210 |