CN109749079A - A kind of degradable polyamide 6 copolymer of biology base and preparation method thereof - Google Patents
A kind of degradable polyamide 6 copolymer of biology base and preparation method thereof Download PDFInfo
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- CN109749079A CN109749079A CN201811414114.5A CN201811414114A CN109749079A CN 109749079 A CN109749079 A CN 109749079A CN 201811414114 A CN201811414114 A CN 201811414114A CN 109749079 A CN109749079 A CN 109749079A
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Abstract
The present invention relates to degradable polyamide 6 copolymers of a kind of biology base and preparation method thereof, method are as follows: synthesize the polyamide 6 performed polymer of binary acid blocked first, then biology base dihydric alcohol, which is added, makes it react obtained polyamide 6 performed polymer carboxylate with the carboxyl of end group, ester exchange reaction is carried out after finally mixing polyamide 6 performed polymer carboxylate with biology base polyester, the degradable polyamide 6 copolymer of biology base is made.The degradable polyamide 6 copolymer molecule chain of biology base obtained is mainly made of biology base dihydric alcohol segment, polyamide 6 performed polymer segment and biology base polyester segment.The present invention is dispersed in biology base dihydric alcohol and biology base polyester block in polyamide 6 performed polymer by the method being copolymerized, and increases the high efficiency of copolymer degradation uniformity and degradation rate.Polyamide 6 copolymer fusing point obtained is high, and hot water extractables content is low, can direct fabrics, fibre strength obtained is good, degradable, it can be achieved that large-scale production, application prospect are good.
Description
Technical field
The invention belongs to high-molecular copolymer preparation technical fields, are related to a kind of degradable polyamide 6 copolymer of biology base
And preparation method thereof.
Background technique
The material of polyamide high molecular polymer preparation has excellent performance, as Fypro has breaking strength
It is high, wearability is good, good hygroscopicity, dyeability are good, elastic recovery rate and the advantages that superior fatigue resistance.Fypro has very
Multi items, principal item are daiamid-6 fiber and Nylon66, can be used for preparing tyre cord, automobile weaving
Product and filtering material etc., have a wide range of application.
But a large amount of the discarded of polyamide high molecular material also bring more serious problem of environmental pollution, therefore, polyamides
The degradability of amine high molecular material is also more and more paid attention to.Biodegradable polymer material refers to by nature
In biological such as bacterium, fungi or algae erosion after can be degradable polymer.The biodegrade of polymer is one
Extremely complex process depends primarily on size and structure, type of microorganism and enzyme of polymer molecule etc..Polyamide 6 master
If being broken specifically by biological enzyme amido bond so that macromolecular chain gradually fragments into small point by bio-enzyme degradation
Subchain (has certain environment degradability), and small molecule chain completes degradation under the catalytic action of biological enzyme, but it has degradation
Period long problem, this is because the content of the catalyzing enzyme of degradable polyamide 6 present in nature is lower and catalyzing enzyme pair
The catalytic efficiency of macromole polyamide 6 is extremely low, therefore its degradation rate is lower.
In addition, preparing polyamide 6 copolymer at present is directly to be copolymerized using small molecule, the segment that copolymer is made is regular
It is poor to spend, since moieties segment can not crystallize so that the fusing point of obtained copolymer is lower or without definite melting point, the lower meeting of fusing point
The application range and difficulty of processing of copolymer are influenced, no definite melting point can make material not have mobility, be unable to satisfy melting and spin
The requirement of silk.It is current that prepare polyamide 6 copolymer be to carry out polycondensation, nitrogen in the case where the protection of normal pressure stream of nitrogen gas
Gas air-flow can only take away water and caprolactam monomer volatile in system, can not remove cyclic oligomer, in addition reaction heating power
The presence of balance is learned, 6~10wt% impurity (unreacted monomer and cyclic oligomer) can be contained in final product.And spinning
Requirement of the process to polyamide 6 copolymer is very high, and as included a large amount of oligomer in copolymer, oligomer will be different in system
It is mutually nucleated, nucleus is constantly grown up in winding drafting process, just will appear stress collection after its crystallite dimension is more than fibre diameter
In to being broken.Meanwhile will affect molecule segment regularity, so that copolymer can not crystallize, in spinning process altogether
Polymers will appear tough section (crystal region) and crisp section (unformed area), and tough section has intensity, and crisp section does not have intensity, lead with after winding
Crisp section of stress concentration will appear fracture of wire during stretching, can not be at fibre, even if will cause fibre at its fiber strength distribution unevenness after fibre
It is low to tie up intensity.Therefore, hydro-thermal extraction removal impurity, and ehter bond, ester in hydro-thermal extraction process in strand need to be carried out to it
Certain hydrothermal degradation occurs for key, this will affect the stability of product.
Therefore, a kind of fusing point is high, stability is good and degradation efficiency the is high degradable polyamide 6 of biology base is studied with important
Meaning.
Summary of the invention
The purpose of the present invention is overcoming defect existing in the prior art, provide that a kind of fusing point is high, stability is good and degradation
Degradable polyamide 6 of high-efficient biology base and preparation method thereof.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of degradable polyamide 6 copolymer of biology base, strand are mainly pre- by biology base dihydric alcohol segment, polyamide 6
Aggressiveness segment and biology base polyester segment are constituted；
The polyamide 6 performed polymer segment is mainly made of caprolactam segment and binary acid end-capping reagent segment.
Transesterification can occur for the ester bond of polyamide 6 copolymer in system under vacuum and exchange target is random, meeting in this way
Generate two kinds of on-link mode (OLM)s: one kind is that the polyamide 6 performed polymer of biological dihydric alcohol sealing end and biology base polyester take off biology base two
Transesterification again after first alcohol；Interreaction is taken off between the polyamide 6 performed polymer of another kind of exactly two biology base dihydric alcohols sealing end
Mutual transesterification after one biology base dihydric alcohol, the first kind react the biology base second taken off on only one performed polymer in segment
Glycol, chain growth are linked not against biology base dihydric alcohol, and the reaction of the second class can then remain next biology base second member alcohol as chain
Group is connect, no matter which kind of chain growth mode can all make the polyamide 6 performed polymer segment end of certain molecular weight link biology in this way
Substratess matter increases the stability of degradation.
As a preferred technical scheme:
A kind of degradable polyamide 6 copolymer of biology base as described above, the degradable polyamide 6 copolymer of biology base
Relative viscosity be 2.4~4.0, hot water extractables content is 0.05~2wt%, and fusing point is 80~210 DEG C, and the prior art is logical
Cross polyamide 6 copolymer made from modification by copolymerization relative viscosity be 1.8~3.0, hot water extractables content be 6~
10wt%, fusing point be 50~180 DEG C or without definite melting point, the fusing point of copolymer of the invention than the prior art it is higher be because
The prior art is mainly to pass through to improve the functionality that reaction active sites quantity i.e. copolymerization component content guarantees copolymer, and this can shadow
The crystallization of copolymer is rung, so that the fusing point of copolymer is greatly reduced or makes copolymer without definite melting point, and the present invention passes through control
The molecular weight of block processed, while being needed not move through by the way of transesterification chain growth and improving end group quantitative commitments polymer
Functionality has no effect on the crystallization of copolymer, and furthermore the present invention also significantly reduces hot water extractables content in copolymer,
So that copolymer of the invention is not necessarily to carry out water hot extraction when carrying out following process, reduce in this process copolymer molecule chain
The hydrothermal degradation of ehter bond and ester bond ensure that the stability of copolymer product；
The filament number of the fiber as made from biology base degradable polyamide 6 copolymer is 0.5~20dtex, breaking strength
For 1.0~2.5cN/dtex, weight-loss ratio is 65~95wt% after burying 6 months in soil, due to the block copolymerization of the prior art
Type polyamide material is higher to spinning processing request, thus can not be applied to fibre field, not have after at fibre
Intensity, block copolymerization type polyamide 6 copolymer obtained by the present invention can be used for preparing fibre, and fiber obtained is disconnected
Resistance to spalling, in addition, burying the method that loss quality is surveyed in degradation using traditional soil, measures inventive article degradation effect up to 1.0~2.5
Good, weight-loss ratio is 65~95wt% after burying 6 months in soil, and weightless part is part of degrading, and high score in the prior art
Sub- polyamide 6 can not degrade；
The number of the polyamide 6 performed polymer segment, biology base polyester segment and the degradable polyamide 6 copolymer of biology base is equal
Molecular weight is respectively 1000~3000,5000~10000 and 15000~28000；The equal molecule of number of polyamide 6 performed polymer segment
The number-average molecular weight of amount and biology base polyester segment can change in a certain range, but changing cannot be too big, number-average molecular weight mistake
The low crystal property that will affect copolymer causes copolymer fusing point too low or can not crystallize its application of influence, number-average molecular weight mistake
It is excessively high that height will cause obtained molecular weight of copolymer；The number-average molecular weight of the degradable polyamide 6 copolymer of biology base can be in certain model
Enclose interior variation, but changing cannot be too big, number-average molecular weight is excessively high, and to will lead into fine processing temperature excessively high, decomposes temperature close to copolymer
Degree causes product to decompose, the too low i.e. number-average molecular weight of polyamide 6 performed polymer segment and biology base polyester segment of number-average molecular weight
It is lower, it will affect the crystal property of copolymer.
A kind of degradable polyamide 6 copolymer of biology base as described above, the biology base dihydric alcohol segment are biology base
Propylene glycol segment and/or biology base pentanediol segment；
The binary acid end-capping reagent segment is HOOC (CH2)nCOOH segment, terephthalic acid (TPA) segment and phthalic acid chain
One or more of section, n are 2~10；
The biology base polyester segment is biology base polyhydroxybutyrate valeric acid copolyesters segment and/or biology base polylactic acid chain
Section.Biological poly hydroxybutyric acid valeric acid copolyesters and biological poly lactic acid are to industrialize more mature product at present, the present invention
Only as example.Biology base polyester of the invention is not limited to that the degradable dihydric alcohol of other biological base and biology base can drop
Solve the equally applicable present invention of polyester.
The present invention also provides a kind of method of the degradable polyamide 6 copolymer of biology base as described above is prepared, close first
At the polyamide 6 performed polymer of binary acid blocked, biology base dihydric alcohol, which is then added, makes it react obtained polyamides with the carboxyl of end group
6 performed polymer carboxylate of amine carries out ester exchange reaction and is made after finally mixing polyamide 6 performed polymer carboxylate with biology base polyester
The degradable polyamide 6 copolymer of biology base.
As a preferred technical scheme:
Method as described above, the specific steps are as follows:
(1) under conditions of temperature is 60~100 DEG C, by caprolactam, binary acid end-capping reagent, deionized water and catalyst
It is mixed to get mixture, the additive amount of binary acid end-capping reagent, deionized water and catalyst is respectively caprolactam additive amount (this hair
Bright all additive amounts all refer to quality additive amount) 5~30wt%, 2~5wt% and 0.1~1wt%；Reaction of the invention
It is to be carried out based on polymer chemistry Step Condensation principle, binary acid is intended for the end-capping reagent i.e. molecular weight tune of Step Condensation
Agent, which is solved, for accurately reconciling polyamide 6 performed polymer molecular weight is added according to the specific requirement of performed polymer molecular weight
Add, catalyst loading can carry out adjustment appropriate according to the actual situation, but adjust amplitude and should not be too large, and adding too much can be led
It causes to gather cruelly, so that the molecular weight distribution of performed polymer can be uneven, properties of product is influenced, when additive amount is too low to greatly prolong reaction
Between, influence efficiency；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 220~300 DEG C, pressure is 0.1~3MPa, and atmosphere is nitrogen, and termination condition is that the number of polyamide 6 performed polymer is divided equally
Son amount is 1000~3000, and terminal amino group content is lower than 1mmol/kg；The equal molecule of number that the present invention passes through control polyamide 6 performed polymer
Amount guarantees its crystal property and then to ensure the crystal property of copolymer too low or the case where without sharp melting point to avoid there is fusing point,
The terminal amino group content of polyamide 6 performed polymer is low, that is, illustrates that the sealing end effect for the binary acid end-capping reagent that the present invention selects is good, polymerization
High conversion rate afterwards；
(3) esterification is carried out after mixing biology base dihydric alcohol with polyamide 6 performed polymer, and polyamide 6 performed polymer ester is made
The molar ratio of compound, the carboxyl functional group of the hydroxy functional group and polyamide 6 performed polymer of biology base dihydric alcohol is 2.01~2.20:
1, since polymerization process biology base dihydric alcohol is likely to remain in pipeline or autoclave body, biology base dihydric alcohol additive amount is needed slightly
It is excessive, but it should not also be added excessively, otherwise can generate the oligomer such as diethylene glycol (DEG), and the temperature of esterification is 220~260 DEG C,
Pressure is 0.01~0.5MPa, and termination condition is that esterification water yield reaches the 95~98% of theoretical water yield；
(4) the obtained biology base of ester exchange reaction is carried out after mixing polyamide 6 performed polymer carboxylate with biology base polyester can
It degrades polyamide 6 copolymer, the temperature of ester exchange reaction is 250~280 DEG C, and pressure is 100Pa hereinafter, the time is 2~4h, raw
The additive amount of object base polyester is 1~50wt% of caprolactam additive amount in step (1)；The additive amount of biology base polyester can basis
Actual conditions (segment ratio and decomposition efficiency) carry out adjustment appropriate, but adjust amplitude and should not be too large, if additive amount is more than in oneself
The 50wt% of amide additive amount will lead to the decline of copolymer crystal property and fusing point.
Method as described above, which is characterized in that in step (1), when mixing accompanies by mechanical stirring, churned mechanically
Revolving speed is 60~240r/min, and the time is 10~60min；
The binary acid end-capping reagent is HOOC (CH2)nOne or more of COOH, terephthalic acid (TPA) and phthalic acid, n
For 2-10；
The catalyst is polyamide 66 salt and NH2(CH2)xOne or more of COOH, x are 4~10.
Method as described above in step (3), before the esterification starts, is additionally added esterification catalyst；
The additive amount of the esterification catalyst is 10~500ppm of caprolactam additive amount in step (1)；Catalyzing esterification
The additive amount of agent can carry out adjustment appropriate according to the actual situation, but adjust amplitude and should not be too large, and additive amount is very few to be extended instead
Between seasonable, efficiency is reduced, additive amount excessively will lead to that reaction rate is too fast, and reaction profile is uneven；
The esterification catalyst be toluene-4-sulfonic acid, benzene sulfonic acid sodium salt, 6- amino-m-toluene sulfonic acid, phenol 4 sulfonic acid and
One or more of 6- amino-m-toluene sulfonic acid；
The biology base dihydric alcohol is bio-based propylene glycol and/or biology base pentanediol.Biology base dihydric alcohol simultaneously not only limits
In this, biological ethyl glycol etc. is equally applicable to the present invention.
Method as described above in step (4), before the ester exchange reaction starts, is additionally added ester exchange catalyst and anti-
Ether agent；
The ester exchange catalyst and the additive amount of anti-ether agent be respectively biology base polyester additive amount 10~500ppm and
300~500ppm；Additive amount can carry out adjustment appropriate according to the actual situation, but adjust amplitude and should not be too large, catalyst addition
When amount is more than the 500ppm of biology base polyester additive amount, easily occur sudden and violent poly-；
The ester exchange catalyst is Titanium series catalyst and/or antimony-based catalyst, and the anti-ether agent is sodium acetate；
The biology base polyester is made a living object base polyhydroxybutyrate valeric acid copolyesters and/or biological poly lactic acid, and number is divided equally
Son amount is 5000~10000.
Method as described above, the Titanium series catalyst are butyl titanate and/or titanium ethylene glycolate, the antimony-based catalyst
For one or more of antimony oxide, antimony acetate and antimony glycol.
The present invention also provides a kind of preparation methods of the degradable daiamid-6 fiber of biology base, and above-mentioned biology base is degradable
Polyamide 6 copolymer carries out melt spinning and a kind of degradable daiamid-6 fiber of biology base is made, and the technique of the melt spinning is
FDY, UDY, POY, HOY or BCF technique.
As a preferred technical scheme:
A kind of preparation method of the degradable daiamid-6 fiber of biology base as described above, FDY technique specifically:
The obtained degradable polyamide 6 copolymer of biology base, can be immediately according to 6 spinning work of nylon after ester exchange reaction
Skill direct fabrics, 240~280 DEG C of spinning temperature, the first draw-off godet speed is 4000~4500m/min, second spinning reel speed
For 5000~6000m/min, draw ratio is 1.1~1.5 times, and cooling wind temperature is 15~25 DEG C, 0.5~1m/s of wind speed, relatively
Humidity is 60%~90%, obtains fully drawn yarn；
UDY technique specifically:
The obtained degradable polyamide 6 copolymer of biology base, can be immediately according to 6 spinning work of nylon after ester exchange reaction
Skill direct fabrics, spinning temperature are 240~280 DEG C, and spinning speed is 700~1500m/min, and cooling wind temperature is 20~30 DEG C,
0.3~1m/s of wind speed, relative humidity are 60%~80%, obtain non-oriented silk；
POY technique specifically:
The obtained degradable polyamide 6 copolymer of biology base, can be immediately according to 6 spinning work of nylon after ester exchange reaction
Skill direct fabrics, spinning temperature are 240~280 DEG C, and spinning speed is 4000~4500m/min, and cooling wind temperature is 15~25 DEG C,
0.3~0.6m/s of wind speed, relative humidity are 60%~80%, obtain preoriented yarn；
HOY technique specifically:
The obtained degradable polyamide 6 copolymer of biology base, can be immediately according to 6 spinning work of nylon after ester exchange reaction
Skill direct fabrics, spinning temperature are 240~280 DEG C, and spinning speed is 4500~6000m/min, and cooling wind temperature is 15~20 DEG C,
0.3~0.5m/s of wind speed, relative humidity are 80%~90%, obtain high oriented yarn；
BCF technique specifically:
The obtained degradable polyamide 6 copolymer of biology base, can be immediately according to 6 spinning work of nylon after ester exchange reaction
Skill direct fabrics obtain AIRJET TEXTURING YARN, and spinning temperature is 240~280 DEG C, and cooling wind temperature is 20~30 DEG C, 0.3~1m/ of wind speed
S, relative humidity are 60%~80%, and feeding roll temperature is 60~120 DEG C, and draw roll temperature is 100~190 DEG C, feeding speed
For 300~1000m/min, tensile speed is 1000~3500m/min, and draw ratio is 3.5~5 times, deforms hot air temperature
It is 190~230 DEG C, air injection pressure is 196KPa~490KPa, and winding speed is 600~3000m/min, cooling air temperature
Degree is 25 DEG C.
Invention mechanism:
The preparation method that the present invention prepares the degradable polyamide 6 copolymer of biology base is to synthesize gathering for binary acid blocked first
6 performed polymer of amide, biology base dihydric alcohol, which is then added, makes it react obtained polyamide 6 performed polymer carboxylate with the carboxyl of end group,
Ester exchange reaction is carried out after finally polyamide 6 performed polymer carboxylate is mixed with biology base polyester, and the degradable polyamides of biology base is made
6 copolymer of amine.
The molecular formula of polyamide 6 performed polymer carboxylate are as follows:
Wherein, a group is divided into polyamide 6 prepolymer segment, and b component is biology base dihydric alcohol, and c group is divided into binary acid.
The molecular formula of the degradable polyamide 6 copolymer of biology base are as follows:
Or
Wherein, A is biology base polyester, and b component is biology base dihydric alcohol, and A realizes polyamide 6 pre-polymerization by transesterification mode
The chain growth of body.
By the present invention in that being blocked and being controlled the molecular weight of performed polymer, to polyamide 6 performed polymer with binary acid to protect
Card performed polymer can promote to crystallize, and ensure that it is formed after copolymer with polyester and be still able to maintain certain crystal property, while this
The molecular weight of invention control biology base polyester carries out copolymerization realization using transesterification principle to guarantee the crystal property of copolymer
Chain growth will not change the structure of its performed polymer segment in this way, and interaction can generate eutectic knot between different crystalline segments
Structure improves the alignment degree of copolymer molecule chain, ensure that the fusing point of copolymer.And the polyamide copolymer of the prior art is equal
It is directly directly to be copolymerized using small molecule, the segment regularity that copolymer is made is poor, and molecule segment can not crystallize, and reduces
Copolymer fusing point causes the copolymer without definite melting point, and segment regularity difference is resulted in will appear in spinning process
Tough section (crystal region) and crisp section (unformed area), tough section has intensity, and crisp section does not have intensity, crisp during winding and first break draft
Easily there is fracture of wire in Duan Yingli concentration, can not be at fibre, can greatly shadow after at fibre due to its fiber strength distribution unevenness
Fibre strength is rung, simultaneously as the relatively low melting point of copolymer, the cooling air channel of traditional device for spinning will can not gather before being reeled up
It is completely cooling to close object, this will lead to fiber and sticks together, and influence it into fibre.The present invention is by improving the regular of copolymer molecule chain
Degree and fusing point overcome prior art polyamide copolymer and are difficult into fine defect.
In addition, existing preparation method is to carry out polycondensation reaction under nitrogen protection under normal pressure, although nitrogen can be taken away
The water and caprolactam monomer of volatilization, but the cyclic oligomer in system can not be removed, and put down simultaneously because thermodynamics of reactions exists
It weighs, it can the hot water extractables (including unreacted monomer and cyclic oligomer) containing 6~10wt% in final products.To overcome
In the prior art copolymer hot water extractables too high levels influence properties of product defect, the present invention in high vacuum conditions into
Copolymer is made in row transesterification, by the small molecule (caprolactam and cyclic oligomer) in the suction removing system of vacuum, though
So there are still thermodynamical equilibriums for reaction, but since the small molecule of extracting is much higher than balance bring small molecule, significantly reduce
Hot water extractables content in copolymer.
The good degrading effect of the degradable polyamide 6 copolymer of biology base of the invention, the present invention is by by bio-based matter
The copolymerization link of polyamide 6 segment is significantly improved the degradation effect of copolymer by (biology base dihydric alcohol and biology base polyester),
In degradation process, since the degradability of biology base segment is better than polyamide 6 segment, will first it degrade, each segment
Degradation sequencing is biology base dihydric alcohol segment → biology base polyester segment → polyamide 6 segment.Due to entire degradation process
Middle macromolecular chain segment resolves into the process time-consuming longest of small molecule segment, present invention introduces biology base segment (biology base binary
Alcohol segment and biology base polyester segment) degradation after, the molecular chain rupture of copolymer, copolymer by a macromolecules degradation be several
Small molecule, small molecule continue to degrade under the catalytic action of biological enzyme, are finally completed biodegrade.The present invention is by introducing biology
Base segment greatly improves the degradation efficiency that copolymer is improved copolymer by the rate that macromolecules degradation is small molecule in turn.
Copolymerization, which is carried out, the present invention is based on transesterification principle realizes chain growth, this is a kind of chain growth mode of random copolymerization,
That is ester exchange reaction can occur for the segment with ester structure.The ester exchange reaction that the present invention process occurs is specific
Are as follows: 1) ester exchange reaction between polyamide 6 performed polymer carboxylate, using intermediate biology base dihydric alcohol as link after reaction
End；2) ester exchange reaction between polyamide 6 performed polymer carboxylate and polyester, polyamide 6 segment and polyester therein after reaction
Segment is linked.No matter which kind of above random copolymerization link can all make between polyamide 6 segment comprising bio-based matter, Bu Huizeng
Add its identical chain segment molecular weight, therefore ensure that the stability of copolymer degradation, copolymer obtained will not be because of polyamide 6 point
The growth of subchain section and lose biological degradability.
The utility model has the advantages that
(1) preparation method of the degradable polyamide 6 copolymer of biology base of the invention, simple process, high production efficiency will
Biology base polyester segment is introduced into polyamide 6 performed polymer, and biodegradability possessed by polyester is dissolved into polyamide 6 base
In body, so that final polyamide 6 base co-polymer obtained has biodegradable ability；
(2) preparation method of the degradable polyamide 6 copolymer of biology base of the invention, polyamide 6 copolymerization in preparation process
The molecular weight and biological poly ester content of object are controllable, can prepare the polyamide 6 copolymer of different degradation speeds；
(3) the degradable polyamide 6 copolymer of biology base of the invention, fusing point is high, and hot water extractables content is low, Ke Yizhi
Row spinning is tapped into, avoids water-heat process more than copolymer fusing point and the application limitation of ehter bond ester bond hydrothermal degradation bring；
(4) the degradable polyamide 6 copolymer of biology base of the invention, the fibrous fracture intensity after spinning is high, biodegrade
Good, the great application prospect of property.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 75 DEG C, by polyamide 66 salt and NH2(CH2)4COOH mixture (mass ratio 1:
1), caprolactam, HOOC (CH2)2COOH and deionized water, which mix and accompany by mechanical stirring, obtains mixture, HOOC (CH2)2The additive amount of COOH is the 11wt% of caprolactam additive amount, and the additive amount of deionized water is caprolactam additive amount
2wt%, polyamide 66 salt and NH2(CH2)4The additive amount of the mixture of COOH is the 0.2wt% of caprolactam additive amount, mechanical
The revolving speed of stirring is 80r/min, time 10min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 220 DEG C, pressure 0.5MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
1000, terminal amino group content 0.2mmol/kg；
(3) esterification is carried out after mixing bio-based propylene glycol, polyamide 6 performed polymer and toluene-4-sulfonic acid to be made
Polyamide 6 performed polymer carboxylate, mole of the carboxyl functional group of the hydroxy functional group and polyamide 6 performed polymer of bio-based propylene glycol
Than being 220 DEG C, pressure 0.22MPa for the temperature of 2.20:1, esterification, termination condition is that esterification water yield reaches reason
By the 95% of water yield, the additive amount of toluene-4-sulfonic acid is the 350ppm of caprolactam additive amount in step (1)；
(4) polyamide 6 performed polymer carboxylate, butyl titanate, sodium acetate and biological poly hydroxybutyric acid valeric acid are copolymerized
Ester exchange reaction is carried out after ester mixing, and the degradable polyamide 6 copolymer of biology base is made, the temperature of ester exchange reaction is 250 DEG C,
Pressure is 90Pa, and time 2h, the additive amount of biological poly hydroxybutyric acid valeric acid copolyesters is caprolactam addition in step (1)
The additive amount of the 20wt% of amount, butyl titanate and sodium acetate is respectively biological poly hydroxybutyric acid valeric acid copolyesters additive amount
300ppm and 300ppm, biological poly hydroxybutyric acid valeric acid copolyesters number-average molecular weight are 5000.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 15000, relative viscosity 3.5, hot water
Extractable is 0.11wt%, and fusing point is 150 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are FDY technique, wherein 240 DEG C of spinning temperature, the first draw-off godet speed is 4000m/min, the
Two draw-off godet speed are 6000m/min, and draw ratio is 1.1 times, and cooling wind temperature is 25 DEG C, wind speed 1m/s, and relative humidity is
60%, obtain the degradable daiamid-6 fiber of fully drawn yarn i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 15dtex, breaking strength 2.3cN/
Dtex, weight-loss ratio is 80wt% after burying 6 months in soil.
Embodiment 2
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 100 DEG C, by polyamide 66 salt and NH2(CH2)6(mass ratio is the mixture of COOH
1:1), caprolactam, HOOC (CH2)3COOH and deionized water, which mix and accompany by mechanical stirring, obtains mixture, HOOC (CH2)3The additive amount of COOH is the 17wt% of caprolactam additive amount, and the additive amount of deionized water is caprolactam additive amount
2.5wt%, polyamide 66 salt and NH2(CH2)6The additive amount of the mixture of COOH is the 0.8wt% of caprolactam additive amount, machine
The revolving speed of tool stirring is 150r/min, time 30min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 280 DEG C, pressure 1.3MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
1500, terminal amino group content 0.5mmol/kg；
(3) esterification is carried out after mixing biology base pentanediol, polyamide 6 performed polymer and benzene sulfonic acid sodium salt, and polyamides is made
6 performed polymer carboxylate of amine, the molar ratio of the hydroxy functional group and the carboxyl functional group of polyamide 6 performed polymer of biology base pentanediol are
2.08:1, the temperature of esterification are 230 DEG C, pressure 0.30MPa, and termination condition reaches theory for esterification water yield and goes out
The 96% of water, the additive amount of benzene sulfonic acid sodium salt are the 10ppm of caprolactam additive amount in step (1)；
(4) ester friendship is carried out after mixing polyamide 6 performed polymer carboxylate, titanium ethylene glycolate, sodium acetate with biological poly lactic acid
It changes reaction and the degradable polyamide 6 copolymer of biology base is made, the temperature of ester exchange reaction is 250 DEG C, pressure 95Pa, and the time is
4h, the additive amount of biological poly lactic acid are the 40wt% of caprolactam additive amount in step (1), and titanium ethylene glycolate and sodium acetate add
Dosage is respectively the 50ppm and 320ppm of biological poly lactic acid additive amount, and biological poly lactic acid number-average molecular weight is 6000.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 22000, relative viscosity 2.8, hot water
Extractable is 0.19wt%, and fusing point is 80 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are FDY technique, wherein 280 DEG C of spinning temperature, the first draw-off godet speed is 4500m/min, the
Two draw-off godet speed are 5000m/min, and draw ratio is 1.5 times, and cooling wind temperature is 15 DEG C, wind speed 0.5m/s, and relative humidity is
90%, obtain the degradable daiamid-6 fiber of fully drawn yarn i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 19dtex, breaking strength 2.0cN/
Dtex, weight-loss ratio is 80wt% after burying 6 months in soil.
Embodiment 3
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 85 DEG C, by caprolactam, HOOC (CH2)5COOH, deionized water and polyamide 66 salt
It mixes and accompanies by mechanical stirring and obtain mixture, HOOC (CH2)5The additive amount of COOH, deionized water and polyamide 66 salt is respectively
5wt%, 4.5wt% and 0.2wt% of caprolactam additive amount, churned mechanically revolving speed are 100r/min, time 60min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 240 DEG C, pressure 2MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
2000, terminal amino group content 0.8mmol/kg；
(3) by the mixture (mass ratio 1:1) of bio-based propylene glycol and biology base pentanediol, polyamide 6 performed polymer with
And esterification is carried out after 6- amino-m-toluene sulfonic acid mixing, polyamide 6 performed polymer carboxylate, bio-based propylene glycol and life is made
The molar ratio of the carboxyl functional group of the hydroxy functional group and polyamide 6 performed polymer of the mixture of object base pentanediol is 2.14:1, ester
The temperature for changing reaction is 250 DEG C, pressure 0.12MPa, and termination condition is that esterification water yield reaches theoretical water yield
The additive amount of 95%, 6- amino-m-toluene sulfonic acid is the 100ppm of caprolactam additive amount in step (1)；
(4) by the mixture (mass ratio 1:1) of butyl titanate and titanium ethylene glycolate, polyamide 6 performed polymer carboxylate, vinegar
Sour sodium carries out ester exchange reaction after mixing with biological poly lactic acid and the degradable polyamide 6 copolymer of biology base is made, and transesterification is anti-
The temperature answered is 260 DEG C, pressure 85Pa, time 4h, and the additive amount of biological poly lactic acid is that caprolactam adds in step (1)
The additive amount of the mixture of the 40wt% of dosage, butyl titanate and titanium ethylene glycolate is the 10ppm of biological base polylactic acid additive amount,
The additive amount of sodium acetate is the 400ppm of biological base polylactic acid additive amount, and biological poly lactic acid number-average molecular weight is 8500.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 19000, relative viscosity 3.3, hot water
Extractable is 1.33wt%, and fusing point is 180 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are POY technique, wherein spinning temperature is 240 DEG C, spinning speed 4500m/min, cooling wind
Temperature is 15 DEG C, wind speed 0.6m/s, and relative humidity 60% obtains the degradable daiamid-6 fiber of preoriented yarn i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 10dtex, breaking strength 1.0cN/
Dtex, weight-loss ratio is 65wt% after burying 6 months in soil.
Embodiment 4
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 75 DEG C, by caprolactam, HOOC (CH2)8COOH, deionized water and NH2(CH2)4COOH, which is mixed and accompanied by mechanical stirring, obtains mixture, HOOC (CH2)8COOH, deionized water and NH2(CH2)4The addition of COOH
Amount is respectively 15wt%, 3wt% and 0.1wt% of caprolactam additive amount, and churned mechanically revolving speed is 60r/min, and the time is
10-60min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 300 DEG C, pressure 0.1MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
1400, terminal amino group content 0.7mmol/kg；
(3) by the mixture (mass ratio 2:1) of bio-based propylene glycol and biology base pentanediol, polyamide 6 performed polymer with
And esterification is carried out after phenol 4 sulfonic acid mixing, polyamide 6 performed polymer carboxylate, bio-based propylene glycol and biology base penta is made
The molar ratio of the carboxyl functional group of the hydroxy functional group and polyamide 6 performed polymer of the mixture of glycol is 2.18:1, esterification
Temperature be 260 DEG C, pressure 0.01MPa, termination condition be esterification water yield reach the 97% of theoretical water yield, benzene
The additive amount of phenol -4- sulfonic acid is the 200ppm of caprolactam additive amount in step (1)；
(4) polyamide 6 performed polymer carboxylate, antimony oxide, sodium acetate and biological poly hydroxybutyric acid valeric acid are total to
Polyester carries out ester exchange reaction after mixing with the mixture (mass ratio 1:1) of biological poly lactic acid and biology base degradable poly is made
6 copolymer of amide, the temperature of ester exchange reaction are 280 DEG C, pressure 80Pa, time 4h, biological poly hydroxybutyric acid valeric acid
The additive amount of the mixture of copolyesters and biological poly lactic acid is the 10wt% of caprolactam additive amount in step (1), three oxidations
The additive amount of two antimony and sodium acetate is respectively that biological poly hydroxybutyric acid valeric acid copolyesters and the mixture of biological poly lactic acid add
The 420ppm and 350ppm of dosage, the equal molecule of mixture number of biological poly hydroxybutyric acid valeric acid copolyesters and biological poly lactic acid
Amount is 10000.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 20000, relative viscosity 2.4, hot water
Extractable is 1.08wt%, and fusing point is 200 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are POY technique, wherein spinning temperature is 280 DEG C, spinning speed 4000m/min, cooling wind
Temperature is 25 DEG C, wind speed 0.3m/s, and relative humidity 80% obtains the degradable daiamid-6 fiber of preoriented yarn i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 18dtex, breaking strength 1.5cN/
Dtex, weight-loss ratio is 70wt% after burying 6 months in soil.
Embodiment 5
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under the conditions of at a temperature of 90 °C, by caprolactam, HOOC (CH2)10COOH, deionized water and NH2(CH2)5COOH, which is mixed and accompanied by mechanical stirring, obtains mixture, HOOC (CH2)10COOH, deionized water and NH2(CH2)5The addition of COOH
Amount is respectively 22wt%, 5wt% and 0.6wt% of caprolactam additive amount, and churned mechanically revolving speed is 190r/min, and the time is
50min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 250 DEG C, pressure 0.6MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
2200, terminal amino group content 0.6mmol/kg；
(3) it carries out being esterified after mixing bio-based propylene glycol, polyamide 6 performed polymer and 6- amino-m-toluene sulfonic acid anti-
Polyamide 6 performed polymer carboxylate, the hydroxy functional group of bio-based propylene glycol and the carboxyl functional group of polyamide 6 performed polymer should be made
Molar ratio be 2.01:1, the temperature of esterification is 250 DEG C, pressure 0.18MPa, and termination condition is esterification water yield
95%, the 6- amino-m-toluene sulfonic acid additive amount for reaching theoretical water yield is caprolactam additive amount in step (1)
300ppm；
(4) polyamide 6 performed polymer carboxylate, antimony acetate, sodium acetate and biological poly hydroxybutyric acid valeric acid copolyesters are mixed
Ester exchange reaction being carried out after conjunction, the degradable polyamide 6 copolymer of biology base being made, the temperature of ester exchange reaction is 260 DEG C, pressure
For 55Pa, time 3h, the additive amount of biological poly hydroxybutyric acid valeric acid copolyesters is caprolactam additive amount in step (1)
The additive amount of 22wt%, antimony acetate and sodium acetate be respectively biological poly hydroxybutyric acid valeric acid copolyesters additive amount 200ppm and
500ppm, biological poly hydroxybutyric acid valeric acid copolyesters number-average molecular weight are 7000.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 23000, relative viscosity 3.0, hot water
Extractable is 2wt%, and fusing point is 210 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are UDY technique, wherein spinning temperature is 280 DEG C, spinning speed 700m/min, cooling wind temperature
It is 30 DEG C, wind speed 0.3m/s, relative humidity 80% obtains the degradable daiamid-6 fiber of non-oriented silk i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 20dtex, breaking strength 1.9cN/
Dtex, weight-loss ratio is 90wt% after burying 6 months in soil.
Embodiment 6
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 65 DEG C, by caprolactam, terephthalic acid (TPA), deionized water and NH2(CH2)7COOH
It mixes and accompanies by mechanical stirring and obtain mixture, terephthalic acid (TPA), deionized water and NH2(CH2)7The additive amount of COOH is respectively
20wt%, 3.5wt% and 0.7wt% of caprolactam additive amount, churned mechanically revolving speed are 210r/min, time 60min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 270 DEG C, pressure 2.5MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
2500, terminal amino group content 0.3mmol/kg；
(3) by the mixture (quality of biology base pentanediol, polyamide 6 performed polymer and toluene-4-sulfonic acid and benzene sulfonic acid sodium salt
Than for 2:1) mixing after carry out esterification be made polyamide 6 performed polymer carboxylate, the hydroxy functional group of biology base pentanediol with
The molar ratio of the carboxyl functional group of polyamide 6 performed polymer is 2.05:1, and the temperature of esterification is 240 DEG C, pressure 0.4MPa,
Termination condition is that esterification water yield reaches the 98% of theoretical water yield, the mixture of toluene-4-sulfonic acid and benzene sulfonic acid sodium salt
Additive amount is the 120ppm of caprolactam additive amount in step (1)；
(4) ester friendship is carried out after mixing polyamide 6 performed polymer carboxylate, antimony glycol, sodium acetate with biological poly lactic acid
It changes reaction and the degradable polyamide 6 copolymer of biology base is made, the temperature of ester exchange reaction is 250 DEG C, pressure 70Pa, and the time is
3h, the additive amount of biological poly lactic acid are the 5wt% of caprolactam additive amount in step (1), and antimony glycol and sodium acetate add
Dosage is respectively the 500ppm and 400ppm of biological poly lactic acid additive amount, and biological poly lactic acid number-average molecular weight is 9000.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 25000, relative viscosity 2.7, hot water
Extractable is 1.5wt%, and fusing point is 100 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are UDY technique, wherein spinning temperature is 240 DEG C, spinning speed 1500m/min, cooling wind
Temperature is 20 DEG C, wind speed 1m/s, and relative humidity 60% obtains the degradable daiamid-6 fiber of non-oriented silk i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 9dtex, breaking strength 2.3cN/
Dtex, weight-loss ratio is 95wt% after burying 6 months in soil.
Embodiment 7
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 80 DEG C, by caprolactam, phthalic acid, deionized water and NH2(CH2)10COOH
It mixes and accompanies by mechanical stirring and obtain mixture, phthalic acid, deionized water and NH2(CH2)10The additive amount of COOH is respectively
30wt%, 2wt% and 0.9wt% of caprolactam additive amount, churned mechanically revolving speed are 240r/min, time 10min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 290 DEG C, pressure 1.8MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
3000, terminal amino group content 0.5mmol/kg；
(3) by the mixed of bio-based propylene glycol, polyamide 6 performed polymer and 6- amino-m-toluene sulfonic acid and phenol 4 sulfonic acid
The obtained polyamide 6 performed polymer carboxylate of esterification, the hydroxyl of bio-based propylene glycol are carried out after closing object (mass ratio 1:1) mixing
The molar ratio of the carboxyl functional group of functional group and polyamide 6 performed polymer is 2.14:1, and the temperature of esterification is 220 DEG C, pressure
For 0.05MPa, termination condition is 98%, the 6- amino-m-toluene sulfonic acid and benzene that esterification water yield reaches theoretical water yield
The additive amount of the mixture of phenol -4- sulfonic acid is the 240ppm of caprolactam additive amount in step (1)；
(4) by the mixture (mass ratio 2:1) of butyl titanate and antimony oxide, polyamide 6 performed polymer carboxylate,
Sodium acetate carries out ester exchange reaction after mixing with biological poly lactic acid and the degradable polyamide 6 copolymer of biology base, transesterification is made
The temperature of reaction is 270 DEG C, pressure 100Pa, time 2.2h, and the additive amount of biological poly lactic acid is in step (1) in oneself
The additive amount of the mixture of the 1wt% of amide additive amount, butyl titanate and antimony oxide is biological base polylactic acid additive amount
330ppm, the additive amount of sodium acetate is the 420ppm of biological base polylactic acid additive amount, and biological poly lactic acid number-average molecular weight is
6000。
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 26000, relative viscosity 4.0, hot water
Extractable is 0.05wt%, and fusing point is 160 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are HOY technique, wherein spinning temperature is 280 DEG C, spinning speed 4500m/min, cooling wind
Temperature is 20 DEG C, wind speed 0.3m/s, and relative humidity 90% obtains the degradable daiamid-6 fiber of high oriented yarn i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 16dtex, breaking strength 2.4cN/
Dtex, weight-loss ratio is 80wt% after burying 6 months in soil.
Embodiment 8
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 60 DEG C, by HOOC (CH2)2(mass ratio is the mixture of COOH and terephthalic acid (TPA)
1:1), caprolactam, deionized water and polyamide 66 salt, which mix and accompanies by mechanical stirring, obtains mixture, HOOC (CH2)2COOH
Additive amount with the mixture of terephthalic acid (TPA), deionized water and polyamide 66 salt is respectively caprolactam additive amount
25wt%, 2.5wt% and 1wt%, churned mechanically revolving speed are 120r/min, time 50min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 300 DEG C, pressure 3MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
1600, terminal amino group content 0.7mmol/kg；
(3) by biology base pentanediol, polyamide 6 performed polymer and toluene-4-sulfonic acid, benzene sulfonic acid sodium salt and 6- amino-first
Esterification is carried out after mixture (mass ratio 1:1:2) mixing of benzene sulfonic acid, and polyamide 6 performed polymer carboxylate, biology base is made
The molar ratio of the carboxyl functional group of the hydroxy functional group and polyamide 6 performed polymer of pentanediol is 2.15:1, the temperature of esterification
It is 230 DEG C, pressure 0.5MPa, termination condition is that esterification water yield reaches the 96% of theoretical water yield, toluene -4- sulphur
The additive amount of acid, benzene sulfonic acid sodium salt and 6- amino-m-toluene sulfonic acid mixture is caprolactam additive amount in step (1)
410ppm；
(4) by the mixture (mass ratio 1:3) of titanium ethylene glycolate and antimony glycol, polyamide 6 performed polymer carboxylate, acetic acid
It is total that the obtained degradable polyamide 6 of biology base of ester exchange reaction is carried out after sodium and the mixing of biological poly hydroxybutyric acid valeric acid copolyesters
Polymers, the temperature of ester exchange reaction are 250 DEG C, pressure 90Pa, time 2h, biological poly hydroxybutyric acid valeric acid copolyesters
Additive amount is the 30wt% of caprolactam additive amount in step (1), and the additive amount of the mixture of titanium ethylene glycolate and antimony glycol is
The 450ppm of biological poly hydroxybutyric acid valeric acid copolyesters additive amount, the additive amount of sodium acetate are biology base polyhydroxybutyrate valeric acid
The 500ppm of copolyesters additive amount, biological poly hydroxybutyric acid valeric acid copolyesters number-average molecular weight are 5000.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 28000, relative viscosity 3.8, hot water
Extractable is 0.72wt%, and fusing point is 80 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are HOY technique, wherein spinning temperature is 240 DEG C, and spinning speed is 6000m/min cooling wind temperature
It is 15 DEG C, wind speed 0.5m/s, relative humidity 80% obtains the degradable daiamid-6 fiber of high oriented yarn i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 0.5dtex, breaking strength 1.0cN/
Dtex, weight-loss ratio is 88wt% after burying 6 months in soil.
Embodiment 9
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 95 DEG C, by HOOC (CH2)10The mixing of COOH, terephthalic acid (TPA) and phthalic acid
Object (mass ratio 2:1), caprolactam, deionized water and NH2(CH2)4COOH, which is mixed and accompanied by mechanical stirring, obtains mixture,
HOOC(CH2)10COOH, deionized water and NH2(CH2)4The additive amount of COOH be respectively caprolactam additive amount 27wt%,
4wt% and 0.4wt%, churned mechanically revolving speed are 90r/min, time 20min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 230 DEG C, pressure 2.4MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
2000, terminal amino group content 0.8mmol/kg；
(3) esterification is carried out after mixing biology base pentanediol, polyamide 6 performed polymer and toluene-4-sulfonic acid to be made
Polyamide 6 performed polymer carboxylate, mole of the carboxyl functional group of the hydroxy functional group and polyamide 6 performed polymer of biology base pentanediol
Than being 250 DEG C, pressure 0.22MPa for the temperature of 2.20:1, esterification, termination condition is that esterification water yield reaches reason
By the 97% of water yield, the additive amount of toluene-4-sulfonic acid is the 500ppm of caprolactam additive amount in step (1)；
(4) by the mixture (mass ratio 2:1) of biological poly hydroxybutyric acid valeric acid copolyesters and biological poly lactic acid, poly-
Ester exchange reaction is carried out after 6 performed polymer carboxylate of amide, butyl titanate and sodium acetate mixing, and biology base degradable poly is made
6 copolymer of amide, the temperature of ester exchange reaction are 280 DEG C, pressure 60Pa, time 2.4h, biological poly hydroxybutyric acid penta
The additive amount of the mixture of sour copolyesters and biological poly lactic acid is the 50wt% of caprolactam additive amount in step (1), metatitanic acid
The additive amount of four butyl esters and sodium acetate is respectively the mixture of biological poly hydroxybutyric acid valeric acid copolyesters and biological poly lactic acid
Additive amount 30ppm and 330ppm, the number of the mixture of biological poly hydroxybutyric acid valeric acid copolyesters and biological poly lactic acid
Average molecular weight is 5000.
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 17000, relative viscosity 3.7, hot water
Extractable is 1.65wt%, and fusing point is 210 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are BCF technique, wherein spinning temperature is 280 DEG C, and cooling wind temperature is 20 DEG C, wind speed 1m/s, phase
It is 60% to humidity, feeding roll temperature is 120 DEG C, and draw roll temperature is 100 DEG C, feeding speed 1000m/min, tensile speed
For 1000m/min, draw ratio is 5 times, and deformation hot air temperature is 190 DEG C, air injection pressure 490KPa, winding speed
For 600m/min, cooling air temperature is 25 DEG C, obtains the degradable daiamid-6 fiber of AIRJET TEXTURING YARN i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 2dtex, breaking strength 2.5cN/
Dtex, weight-loss ratio is 65wt% after burying 6 months in soil.
Embodiment 10
A kind of preparation method of the degradable polyamide 6 copolymer of biology base, the specific steps are as follows:
(1) under conditions of temperature is 100 DEG C, caprolactam, terephthalic acid (TPA), deionized water and polyamide 66 salt are mixed
Merging accompanies by mechanical stirring and obtains mixture, and the additive amount of terephthalic acid (TPA), deionized water and polyamide 66 salt is respectively interior
8wt%, 5wt% and 0.1wt% of amide additive amount, churned mechanically revolving speed are 220r/min, time 30min；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, prepolymerization
Temperature be 220 DEG C, pressure 0.1MPa, atmosphere is nitrogen, and termination condition is that the number-average molecular weight of polyamide 6 performed polymer is
2400, terminal amino group content 0.4mmol/kg；
(3) it carries out being esterified after mixing bio-based propylene glycol, polyamide 6 performed polymer and 6- amino-m-toluene sulfonic acid anti-
Polyamide 6 performed polymer carboxylate, the hydroxy functional group of bio-based propylene glycol and the carboxyl functional group of polyamide 6 performed polymer should be made
Molar ratio be 2.15:1, the temperature of esterification is 260 DEG C, pressure 0.1MPa, and termination condition is esterification water yield
96%, the 6- amino-m-toluene sulfonic acid additive amount for reaching theoretical water yield is caprolactam additive amount in step (1)
440ppm；
(4) ester is carried out after mixing polyamide 6 performed polymer carboxylate, antimony oxide, sodium acetate with biological poly lactic acid
The degradable polyamide 6 copolymer of biology base is made in exchange reaction, and the temperature of ester exchange reaction is 280 DEG C, pressure 95Pa, the time
For 3.5h, the additive amount of biological poly lactic acid is the 40wt% of caprolactam additive amount in step (1), antimony oxide and acetic acid
The additive amount of sodium is respectively the 250ppm and 440ppm of biological poly lactic acid additive amount, and biological poly lactic acid number-average molecular weight is
10000。
The number-average molecular weight of the degradable polyamide 6 copolymer of biology base obtained is 24000, relative viscosity 4.0, hot water
Extractable is 2wt%, and fusing point is 160 DEG C.
The degradable polyamide 6 copolymer of biology base obtained is subjected to melt spinning and prepares the degradable polyamide 6 of biology base
Fiber, the technique of melt spinning are BCF technique, wherein spinning temperature is 240 DEG C, and cooling wind temperature is 30 DEG C, wind speed 0.3m/s,
Relative humidity is 80%, and feeding roll temperature is 60 DEG C, and draw roll temperature is 190 DEG C, feeding speed 300m/min, tensile speed
For 3500m/min, draw ratio is 3.5 times, and deformation hot air temperature is 230 DEG C, air injection pressure 196KPa, winding speed
Degree is 3000m/min, and cooling air temperature is 25 DEG C, obtains the degradable daiamid-6 fiber of AIRJET TEXTURING YARN i.e. biology base.
The filament number of the degradable daiamid-6 fiber of final biology base obtained is 15dtex, breaking strength 2.2cN/
Dtex, weight-loss ratio is 70wt% after burying 6 months in soil.
Claims (10)
1. a kind of degradable polyamide 6 copolymer of biology base, it is characterized in that: strand is mainly by biology base dihydric alcohol segment, poly-
6 performed polymer segment of amide and biology base polyester segment are constituted；
The polyamide 6 performed polymer segment is mainly made of caprolactam segment and binary acid end-capping reagent segment.
2. the degradable polyamide 6 copolymer of a kind of biology base according to claim 1, which is characterized in that biology base can drop
Solve polyamide 6 copolymer relative viscosity be 2.4~4.0, hot water extractables content be 0.05~2wt%, fusing point be 80~
210℃；
The filament number of the fiber as made from biology base degradable polyamide 6 copolymer is 0.5~20dtex, and breaking strength is
1.0~2.5cN/dtex, weight-loss ratio is 65~95wt% after burying 6 months in soil.
3. the degradable polyamide 6 copolymer of a kind of biology base according to claim 1, which is characterized in that the polyamide 6
The number-average molecular weight of performed polymer segment, biology base polyester segment and the degradable polyamide 6 copolymer of biology base is respectively 1000~
3000,5000~10000 and 15000~28000.
4. the degradable polyamide 6 copolymer of a kind of biology base according to claim 1, which is characterized in that the biology base
Dihydric alcohol segment is bio-based propylene glycol segment and/or biology base pentanediol segment；
The binary acid end-capping reagent segment is HOOC (CH2)nIn COOH segment, terephthalic acid (TPA) segment and phthalic acid segment
More than one, n be 2~10；
The biology base polyester segment is biology base polyhydroxybutyrate valeric acid copolyesters segment and/or biology base polylactic acid chain segment.
5. the preparation such as a kind of described in any item methods of the degradable polyamide 6 copolymer of biology base of Claims 1 to 4, special
Sign is: synthesizing the polyamide 6 performed polymer of binary acid blocked first, biology base dihydric alcohol, which is then added, keeps it anti-with the carboxyl of end group
Polyamide 6 performed polymer carboxylate should be made, ester friendship is carried out after finally mixing polyamide 6 performed polymer carboxylate with biology base polyester
It changes reaction and the degradable polyamide 6 copolymer of biology base is made.
6. according to the method described in claim 5, it is characterized in that, specific step is as follows:
(1) under conditions of temperature is 60~100 DEG C, caprolactam, binary acid end-capping reagent, deionized water and catalyst are mixed
Obtain mixture, the additive amount of binary acid end-capping reagent, deionized water and catalyst be respectively caprolactam additive amount 5~
30wt%, 2~5wt% and 0.1~1wt%；
(2) mixture is subjected to the polyamide 6 performed polymer that binary acid blocked is made in prepolymerization, the temperature of prepolymerization
Degree is 220~300 DEG C, and pressure is 0.1~3MPa, and atmosphere is nitrogen, and termination condition is the number-average molecular weight of polyamide 6 performed polymer
It is 1000~3000, terminal amino group content is lower than 1mmol/kg；
(3) esterification is carried out after mixing biology base dihydric alcohol with polyamide 6 performed polymer, and the esterification of polyamide 6 performed polymer is made
Object, the molar ratio of the carboxyl functional group of the hydroxy functional group and polyamide 6 performed polymer of biology base dihydric alcohol are 2.01~2.20:1,
The temperature of esterification is 220~260 DEG C, and pressure is 0.01~0.5MPa, and termination condition is that esterification water yield reaches reason
By the 95~98% of water yield；
(4) it is degradable that the obtained biology base of ester exchange reaction is carried out after mixing polyamide 6 performed polymer carboxylate with biology base polyester
Polyamide 6 copolymer, the temperature of ester exchange reaction are 250~280 DEG C, and pressure is 100Pa hereinafter, the time is 2~4h, biology base
The additive amount of polyester is 1~50wt% of caprolactam additive amount in step (1).
7. according to the method described in claim 6, it is characterized in that, in step (1), when mixing, accompanies by mechanical stirring, machine
The revolving speed of tool stirring is 60~240r/min, time 10-60min；
The binary acid end-capping reagent is HOOC (CH2)nOne or more of COOH, terephthalic acid (TPA) and phthalic acid, n 2-
10；
The catalyst is polyamide 66 salt and NH2(CH2)xOne or more of COOH, x are 4~10.
8. according to the method described in claim 6, it is characterized in that, before the esterification starts, being additionally added in step (3)
Esterification catalyst；
The additive amount of the esterification catalyst is 10~500ppm of caprolactam additive amount in step (1)；
The esterification catalyst is toluene-4-sulfonic acid, benzene sulfonic acid sodium salt, 6- amino-m-toluene sulfonic acid, phenol 4 sulfonic acid and 6- ammonia
One or more of base-m-toluene sulfonic acid；
The biology base dihydric alcohol is bio-based propylene glycol and/or biology base pentanediol.
9. according to the method described in claim 6, it is characterized in that, in step (4), before the ester exchange reaction starts, also plus
Enter ester exchange catalyst and anti-ether agent；
The ester exchange catalyst and the additive amount of anti-ether agent be respectively biology base polyester additive amount 10~500ppm and 300~
500ppm；
The ester exchange catalyst is Titanium series catalyst and/or antimony-based catalyst, and the anti-ether agent is sodium acetate；
The biology base polyester is made a living object base polyhydroxybutyrate valeric acid copolyesters and/or biological poly lactic acid, number-average molecular weight
It is 5000~10000.
10. according to the method described in claim 9, it is characterized in that, the Titanium series catalyst is butyl titanate and/or second two
Alcohol titanium, the antimony-based catalyst are one or more of antimony oxide, antimony acetate and antimony glycol.
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