CN104130365B - A kind of linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA and its preparation method and application - Google Patents
A kind of linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA and its preparation method and application Download PDFInfo
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- CN104130365B CN104130365B CN201410350977.6A CN201410350977A CN104130365B CN 104130365 B CN104130365 B CN 104130365B CN 201410350977 A CN201410350977 A CN 201410350977A CN 104130365 B CN104130365 B CN 104130365B
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Abstract
The invention discloses linear polyurethane elastic body toughening agent of a kind of toughness reinforcing Biopolvester PHA and its preparation method and application, belong to toughness reinforcing biodegradable polyesters field.The present invention by polycaprolactone diols, 1; 4 butanediols use without catalyst one-step synthesis with isophorone diisocyanate; under conditions of evacuation or nitrogen are protected; inject mould; in vacuum drying oven, complete chain extending reaction, be prepared for the degradable polyurethane elastic body toughening agent of different hard segment content；Its application is the PU mixing by the biodegradable polyesters PHA of industrialized production with synthesized different hard segment contents, adds solvent, uses solution-casting method, supersound process and with shaking table by it mix homogeneously, injection mould film forming.Compared with pure fragility PHA, the elongation at break of PHA/PU laminated film is greatly increased, and the PU of difference hard segment content all has obvious toughening effect to PHA, its comprehensive mechanical property can be made to improve, toughness significantly improves, and opens new way for expanding the actual application of PHA class material further.
Description
Technical field
The present invention relates to toughness reinforcing biodegradable polyesters, be specifically related to the linear polyurethane of a kind of toughness reinforcing Biopolvester PHA
Elastic body toughening agent and its preparation method and application.
Background technology
Biodegradable material derives from nature, uses and can revert to again nature after discarding, has good ecology
Environment compatibility and development potentiality.In numerous bio-based materials, polyhydroxyalkanoate is because of its totally biodegradable
The extremely concern of researchers.Polyhydroxyalkanoate (PHA) is the total of the thermoplastic polyester that synthesized by fermentable of a class
Claiming, main representative is copolymer (PHBV) and the 3-hydroxyl of poly 3-hydroxy butyrate (PHB), 3-hydroxybutyrate and 3-hydroxypentanoic acid
Base butanoic acid and 4 hydroxybutyric acid copolymer (P (3,4) HB).PHA has biodegradable, biocompatibility and the light of excellence
Learning the performances such as activity, this makes it have huge application prospect in terms of medical material, agricultural materials, packaging material.
At present, PHA class material is high except synthesis cost, especially improves 4 hydroxybutyric acid (4HB), 3-hydroxypentanoic acid
(3HV), outside etc. co-monomer content can cause production cost significantly to rise, there is also the defect in performance, as most
PHA molecular structure regularity is higher, easily crystallizes, and degree of crystallinity can reach 80%, and spherocrystal is relatively big, the hardest but also crisp under room temperature, is weak to
Impact；Easily decompose under molten condition, processing temperature narrow range；Poor solvent resistance and hydrophilic are undesirable etc..These defects
The application making PHA is very restricted, so PHA must carry out the physics of necessity, chemical modification, is retaining excellent properties
While overcome its defect so that it is reach the requirement of actual application.In various performance deficiencies, the fragility of PHA is key problem.
Therefore, in the urgent need to the PHA kind polyester material of industrialization synthesis carrying out the modification in terms of effective mechanical property.
For toughness reinforcing PHA material, existing technology is typically to increase flexible comonomer 4 hydroxybutyric acid (4HB), 3-hydroxyl
The ratio of base valeric acid (3HV) etc., or use the method for grafting increase-volume to improve the toughness of PHA material, but thus cause skill
The increasing of art difficulty, process be complicated and the problem such as increase substantially of cost.Select abundant raw material, structure-controllable, low price,
The simple degradable polyurethane of synthetic method is as toughener, the method using simple physical blending, it is ensured that composite
Degradability.So far there are no for the polyurethane toughened PHA of polycaprolactone diols (PCL) base degradable of the different hard segment content of utilization
Report, significant to the PHA based composites of the excellence preparing mechanical property.
Additionally, the preparation of polyurethane uses pre-polymerization synthetic method mostly at present, catalyst need to be added in building-up process, and need
The extent of reaction of test NCO (NCO), in order to determine that the addition chain extender time completes follow-up chain extending reaction, the method work
Complex and catalyst the addition of sequence often makes the mechanical property of synthesis of polyurethane have reduction in various degree.Compare and
Speech, uses without the one-step synthesis of catalyst, has simple and easy to do feature, it is investigated read use fresh without catalyst one-step synthesis
Have been reported that, and the polycaprolactone glycol based elastomeric of preparation has the performance of excellence." polyurethane industrial " 2004 volume 19 the 6th
Phase, disclosing the synthesis of Aqueous Polyurethane Dispersions Based on In Different kinds of Polycaprolactone Diols and the periodical literature of performance, it disclose in detail " adopts
With pla-pcl dihydroxylic alcohols (PCL), BDO (BD), isophorone diisocyanate (IPDI), N2Mode completely cuts off air
Heating, at 80～95 DEG C, react 2～4h, chain extension " etc. step；But relative to the present invention is prepared toughness reinforcing Biopolvester PHA's
Linear polyurethane elastic body toughening agent, it uses pre-polymerization legal, by adding catalyst, and employs generation cross-linked structure
Cross-linking agent, the problem using a large amount of toxic organic solvents in synthesis, the polyurethane of synthesis is water-soluble cross-linked structure, catalyst
The membership that adds weaken the mechanical property of polyurethane, cross-linked structure is different from linear polyurethane, and cross-linked structure can only be at organic solvent
In swelling, and the polyurethane of linear structure is soluble in organic solvent, and this is to synthetic linear structure PU of the present invention, uses molten
Liquid casting prepares laminated film toughness reinforcing Biopolvester PHA particular importance.
Summary of the invention
1. invention to solve the technical problem that
Mostly use pre-polymerization synthetic method for the preparation of polyurethane in prior art, catalysis need to be added in building-up process
Agent, and the extent of reaction of NCO (NCO) need to be tested, in order to determine that the addition chain extender time completes follow-up chain extending reaction,
And the Biopolvester PHA brittleness problems of existing industrialized production；The present invention provides the line style of a kind of toughness reinforcing Biopolvester PHA to gather
Urethane elastic body toughening agent and its preparation method and application, solves the brittleness problems of PHA class material, and the method is mainly by system
Degradable polyurethane elastic body toughening agent (PU) of standby different hard segment contents as filler, toughness reinforcing Biodegradable polyester PHA class
Material, to expand the application of Biodegradable polyester.
2. technical scheme
For achieving the above object, technical scheme is as follows:
The preparation method of the linear polyurethane elastic body toughening agent of a kind of toughness reinforcing Biopolvester PHA, comprises the steps:
According to the hard segment content of the linear polyurethane elastic body toughening agent synthesizing toughness reinforcing Biopolvester PHA, accurate measurement is
Dried polycaprolactone diols, BDO join in there-necked flask together with isophorone diisocyanate, adopt
With evacuation or logical N2Mode completely cuts off air, with oil bath heating method be heated to 60～80 DEG C, magnetic agitation, reaction 2～
After 3h, reactant liquor is proceeded to mould, put into vacuum drying oven carry out at a temperature of 100～125 DEG C chain extension, deaeration, solidification 12～
Take out after 24h, obtain the linear polyurethane elastic body toughening agent that hard segment content is 35%～60%, described recipe calculation formula
As follows:
WIPDI/MIPDI=WPCL/MPCL+WBD/MBD,
Polycaprolactone diols in described step, its molecular weight is between 1000～3000；Described dry polycaprolactone
Dihydroxylic alcohols, is dried by vacuum drying oven, baking temperature 50～70 DEG C, drying time 24～48h.
In described step, hard segment content is the linear polyurethane elastic body toughening agent of 35%～60%, its total NCO
Mol ratio NCO:OH=1:1 with total hydroxyl.This formula is different from a certain feed molar ratio mistake in the synthesis of general polyurethane
The feature of amount, by first determining hard segment content, can be calculated related raw material consumption proportion.
W in stepIPDI, WPCL, WBDIt is respectively isophorone diisocyanate, polycaprolactone diols and BDO
Quality；MIPDI, MPCL, MBDIt is respectively isophorone diisocyanate, polycaprolactone diols and mole matter of 1,4-butanediol
Measuring, it is respectively 222.29g/mol, and 1000～3000g/mol and 90.12g/mol.
The linear polyurethane elastic body toughening agent of preparation-obtained toughness reinforcing Biopolvester PHA, its structural formula is:
；
Wherein n represents the degree of polymerization of polycaprolactone diols (PCL) raw material, and n is between 10～30.Polymerization degree n is according to institute
Depending on the molecular weight of the polycaprolactone diols (PCL) selected, owing to PCL molecular weight is 1000～3000, therefore n is 10～30
Between.The linear polyurethane elastic body toughening agent of described toughness reinforcing Biopolvester PHA is line style degradation material.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA, by the toughness reinforcing Biopolvester PHA of preparation
Linear polyurethane elastic body toughening agent as toughener for the preparation method of biodegradable polyesters PHA laminated film, its
Step is:
(1) linear polyurethane elastic body toughening agent and the PHA powder of the toughness reinforcing Biopolvester PHA prepared are mixed,
Then mixture is dissolved in chloroform, after supersound process 5～10min, is placed on shaking table at a temperature of 25～40 DEG C and mixes 12
～24h, it is allowed to mix homogeneously；
(2) mixture solution that step (1) mix homogeneously obtains is cast in mould, after solvent at room temperature volatilization, 30
～be vacuum dried at a temperature of 50 DEG C, obtain laminated film.
Described PHA powder is biodegradable polyesters PHA powder, including the poly 3-hydroxy butyrate of feature of enbrittling
(PHB), low 4HB content 3HB4HB copolymer (P (3,4) HB) or low 3HV content 3HB3HV copolymer (PHBV).
The linear polyurethane elastic body toughening agent of described synthesis toughness reinforcing Biopolvester PHA and the mixing of PHA powder, keep total matter
Measuring constant, change the mass ratio of mixture, PHA/PU mass ratio is 70-95:5-30.
Described PHA raw material is provided by different company, crisp including having of Ningbo Tianan Biological Material Co., Ltd.'s production
The poly 3-hydroxy butyrate (PHB) of property feature, the copolymer (PHBV) of 3-hydroxybutyrate and 3-hydroxypentanoic acid and Tianjin state rhythm
The 3-hydroxybutyrate of biomaterial company limited production and 4 hydroxybutyric acid copolymer (P (3,4) HB).
Polyurethane elastomer (the linear polyurethane bullet of toughness reinforcing Biopolvester PHA of the different hard segment contents of described synthesis
Gonosome toughener) it is degradation material, its soft section is polycaprolactone diols (PCL), and hard section consists of isophorone two isocyanide
Acid esters (IPDI) and 1,4-butanediol (BD).
3. beneficial effect
Compared with prior art, the Biopolvester PHA brittleness problems that the present invention is directed to existing industrialized production provides one
Effectively method for toughening, is characterized in that with degradable polycaprolactone diols (PCL) be soft section, with isophorone diisocyanate
(IPDI) it is hard section with BDO (BD), without the synthesis degradable poly of different hard segment contents of catalyst one-step method simplicity
Urethane elastomeric material is as toughener, by it and fragility PHA class material mixing, uses solution-casting method, pours into a mould film forming, obtain
The laminated film of different formulations, mechanical property shows, in certain limit, the PU of different hard segment contents is respectively provided with toughness reinforcing effect to PHA
Really, the purer PHA of mechanical property of PHA/PU laminated film all has improvement in various degree, especially toughness to be improved, disconnected
Split percentage elongation and can reach about 600%.
The invention have the benefit that
(1) the invention provides a kind of method preparing polyurethane elastomer of simple uniqueness, accurate measurement proportioning, use
One-step synthesis without catalyst, first low temperature synthesis, rear high-temperature vacuum chain extension, it is successfully prepared the degradable line of different hard segment content
Type polyurethane elastomer；Raw material used by Tong Shi is less, and several raw materials are simultaneously introduced reactor reaction, it is not necessary to add poisonous
Organic solvent, economic and environment-friendly, directly pour reactant liquor into mould vacuum drying oven chain extension, deaeration after reaction a period of time, obtain
Bright product.
(2) raw material of synthesis of polyurethane is simple, keeps the uniqueness that mol ratio is 1:1 of total NCO and total hydroxyl
Formula, by the hard segment content of presetting required synthesis PU, calculates corresponding raw materials quality, obtains joining of differential responses material amount
Ratio, has prepared the polyurethane elastomer of linear structure, can be completely dissolved in organic solvent, it is simple to solution-casting method preparation is multiple
Close thin film.
(3) PU prepared by is the polyurethane of linear structure, without cross-linked structure, it is ensured that it can be with to use solution-casting method
Being sufficiently mixed of PHA matrix, rather than can only be swelling, it is particularly important that solution-casting method is prepared composite by this point.
(4) biodegradable laminated film prepared by the present invention has good mechanical property, and polyurethane filler is at matrix
In be uniformly dispersed, orientation fibroblast phenomenon in drawing process and molecule interchain avulse effect, substantially increase biodegradable
The toughness of polyester.
(5) present invention is prepared for the polyurethane elastomer of different hard segment content, relates to different hard segment content polyurethane
Tough dose of toughness reinforcing PHA material, provides new approaches and new method for the preparation of toughness reinforcing fragile material.
(6) present invention, avoiding thermal degradation problems serious in the processing of Biopolvester conventional thermal, by the poly-ammonia of different ratio
Ester mixes with PHA powder, uses solution-casting method to prepare composite, and the laminated film internal composition dispersion prepared is all
Even, there is the features such as good toughness and degradable.
(7) solution-casting method is prepared for biodegradable PHA/PU thin film, for expand Biopolvester medical application and
The preparation such as solvent spinning has the fiber of premium properties and has reference value, and PCL base degradable polyurethane elastomer is toughness reinforcing simultaneously
The research and development of PHA class material, has important theoretical direction effect and application for expanding the application of PHA class material further
It is worth.
Accompanying drawing explanation
Fig. 1 is the chemical equation of the present invention used one-step synthesis method PU.
Fig. 2 is that the linear polyurethane elastomer of the employing one-step synthesis method toughness reinforcing Biopolvester PHA of embodiment 2 present invention increases
The infrared spectrum of tough dose；Wherein IPDI is at 2240cm-1The N=C=O peak at place disappears in the collection of illustrative plates after one-step synthesis method PU, with
Time PU infrared at 1528cm-1Place occurs in that the CHN vibration peak relevant to carbamate, at 3300-3400cm-1Place occurs
The infrared peak of N-H indicates IPDI and has completely reacted, and one-step method successfully synthesizes degradable PU elastomer.
Fig. 3 is embodiments of the invention 2 composite extension test mechanical performance data result figures；Wherein abscissa is for stretching
Long rate；Vertical coordinate is intensity.
Fig. 4 is embodiments of the invention 2 composite extension test mechanical performance data tables；
Fig. 5 is that the section before and after the embodiment of the present invention 2 toughening thin film compares SEM photograph；Wherein figure a is that pure P (3,4) HB exists
Brittle failure face in liquid nitrogen, figure b is P (3,4) HB-30 brittle failure face in liquid nitrogen, and figure c is the section after pure P (3,4) HB stretching,
Figure d is the section after P (3,4) HB-30 stretching；Illustrate that the section of pure P (3,4) HB presents more smooth configuration of surface, and answer
Closing the brittle failure of thin film and rougher configuration of surface all occurs in tension failure, tension failure occurs hole and wire drawing fibroblast especially
Phenomenon, illustrates that polyurethane there occurs orientation effect in matrix in drawing process, and intermolecular entanglement makes combining of composite
Conjunction mechanical property improves.
In Fig. 6, figure a, b are configuration of surface SEM in the embodiment of the present invention before and after laminated film P (3,4) HB-5 degraded respectively
Photo；Before degraded, film surface has a lot of micropore, and the aperture stayed after volatilizing for solvent, the thin film after degraded then presents more
The macroscopic void of 50um, and film surface presents, it is biphase that light and shade is evenly distributed, and illustrates that polyurethane is uniformly dispersed in the base, for
Thin film mechanical performance provides microcosmic foundation.
In figure: P (3,4) HB, P (3,4) HB-5, P (3,4) HB-10, P (3,4) HB-20, P (3,4) HB-30 represents respectively
Be not added with pure P (3,4) the HB thin film of polyurethane of synthesis, and P (3,4) HB/PU mass ratio be 95:5,90:10,80:20 and
Laminated film prepared by 70:30.
Detailed description of the invention:
Embodiment 1:
The preparation method of the linear polyurethane elastic body toughening agent of a kind of toughness reinforcing Biopolvester PHA, comprises the steps: pre-
Surely the hard segment content 35% of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA is synthesized, according to recipe calculation formula
The most dried polycaprolactone diols of accurate measurement (PCL, molecular weight 1000) 10g and BDO (BD) 0.9129g with
Isophorone diisocyanate (IPDI) 4.4718g joins in there-necked flask together, uses evacuation mode to completely cut off air, uses
The method of oil bath heating is heated to 80 DEG C, magnetic agitation, after reaction 2h, reactant liquor is proceeded to mould, puts into vacuum drying oven 125
Carry out chain extension, deaeration at a temperature of DEG C, take out after solidification 12h, obtain the linear polyurethane elastomer that hard segment content is 35% and increase
Tough dose；Described recipe calculation formula is as follows:
WIPDI/MIPDI=WPCL/MPCL+WBD/MBD,
Polycaprolactone diols in described step, its molecular weight is 1000；Described dry polycaprolactone diols, passes through
Vacuum drying oven is dried, baking temperature 70 DEG C, drying time 24h.
In described step, hard segment content is the linear polyurethane elastic body toughening agent of 35%, its total NCO and total hydroxyl
Mol ratio NCO:OH=1:1 of base.This formula is different from the spy of a certain feed molar ratio excess in the synthesis of general polyurethane
Levy, by first determining hard segment content, related raw material consumption proportion can be calculated.
W in stepIPDI, WPCL, WBDIt is respectively isophorone diisocyanate, polycaprolactone diols and BDO
Quality；MIPDI, MPCL, MBDIt is respectively isophorone diisocyanate, polycaprolactone diols and mole matter of 1,4-butanediol
Amount, it is respectively 222.29g/mol, 1000g/mol and 90.12g/mol.
Using chemical equation such as Fig. 1 of one-step synthesis method PU, the line style of preparation-obtained toughness reinforcing Biopolvester PHA is gathered
Urethane elastic body toughening agent (is called for short PU)；Its structural formula is:
；
Wherein n represents the degree of polymerization of polycaprolactone diols (PCL) raw material, and n is between 10～30.Polymerization degree n is according to institute
Depending on the molecular weight of the polycaprolactone diols (PCL) selected, owing to PCL molecular weight is 1000, therefore n is 10.Described increasing
The linear polyurethane elastic body toughening agent of tough Biopolvester PHA is line style degradation material.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA, the steps include:
(1) the linear polyurethane elastic body toughening agent of the toughness reinforcing Biopolvester PHA prepared is weighed 0.05g, 0.1g,
0.2g, 0.3g respectively with 0.95g, 0.9g, 0.8g, 0.7gPHA powder mixes, then mixture is dissolved in 30mL chloroform, super
After sonication 10min, it is placed on shaking table mixing 24h at a temperature of 40 DEG C, is allowed to mix homogeneously；
One contrast reference test is set simultaneously, i.e. without the polyurethane elastomer toughener of synthesis, prepares pure PHA thin
Film, as the contrast reference of test result.
(2) mixture solution that step 1 mix homogeneously obtains is cast in mould, after solvent at room temperature volatilization, at 30 DEG C
At a temperature of be vacuum dried 24h, obtain laminated film.
Described PHA powder is biodegradable polyesters PHA powder, for the poly 3-hydroxy butyrate of feature of enbrittling
(PHB)。
Polyurethane elastomer (the linear polyurethane bullet of toughness reinforcing Biopolvester PHA of the different hard segment contents of described synthesis
Gonosome toughener) it is degradation material, its soft section is polycaprolactone diols (PCL), and hard section consists of isophorone two isocyanide
Acid esters (IPDI) and 1,4-butanediol (BD).
Embodiment 2:
The preparation method of the linear polyurethane elastic body toughening agent of a kind of toughness reinforcing Biopolvester PHA, comprises the steps: pre-
Surely the hard segment content 45% of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA is synthesized, according to recipe calculation formula
The most dried polycaprolactone diols of accurate measurement (PCL, molecular weight 2000) 10g and BDO (BD) 1.7198g with
Isophorone diisocyanate (IPDI) 6.4622g joins in there-necked flask together, uses evacuation mode to completely cut off air, uses
The method of oil bath heating is heated to 60 DEG C, magnetic agitation, after reaction 3h, reactant liquor is proceeded to mould, puts into vacuum drying oven 100
Carry out chain extension, deaeration at a temperature of DEG C, take out after solidification 24h, obtain the linear polyurethane elastomer that hard segment content is 45% and increase
Tough dose；Described recipe calculation formula is as follows:
WIPDI/MIPDI=WPCL/MPCL+WBD/MBD,
Polycaprolactone diols in described step, its molecular weight is 2000；Described dry polycaprolactone diols, passes through
Vacuum drying oven is dried, baking temperature 50 DEG C, drying time 48h.
In described step, hard segment content is the linear polyurethane elastic body toughening agent of 45%, its total NCO and total hydroxyl
Mol ratio NCO:OH=1:1 of base.This formula is different from the spy of a certain feed molar ratio excess in the synthesis of general polyurethane
Levy, by first determining hard segment content, related raw material consumption proportion can be calculated.
W in stepIPDI, WPCL, WBDIt is respectively isophorone diisocyanate, polycaprolactone diols and BDO
Quality；MIPDI, MPCL, MBDIt is respectively isophorone diisocyanate, polycaprolactone diols and mole matter of 1,4-butanediol
Amount, it is respectively 222.29g/mol, 2000g/mol and 90.12g/mol.
Using chemical equation such as Fig. 1 of one-step synthesis method PU, the line style of preparation-obtained toughness reinforcing Biopolvester PHA is gathered
Urethane elastic body toughening agent；Its structural formula is:
；
Wherein n represents the degree of polymerization of polycaprolactone diols (PCL) raw material, and n is between 10～30.Polymerization degree n is according to institute
Depending on the molecular weight of the polycaprolactone diols (PCL) selected, owing to PCL molecular weight is 2000, therefore n is 20.Described increasing
The linear polyurethane elastic body toughening agent of tough Biopolvester PHA is line style degradation material.If Fig. 2 is embodiment 2 present invention
Use the infrared spectrum of the linear polyurethane elastic body toughening agent of one-step synthesis method toughness reinforcing Biopolvester PHA.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA, the steps include:
(1) the linear polyurethane elastic body toughening agent of the toughness reinforcing Biopolvester PHA prepared is weighed 0.05g, 0.1g,
0.2g, 0.3g respectively with 0.95g, 0.9g, 0.8g, 0.7gPHA powder mixes, then mixture is dissolved in 50mL chloroform, super
After sonication 5min, it is placed on shaking table mixing 12h at a temperature of 25 DEG C, is allowed to mix homogeneously；
One contrast reference test is set simultaneously, i.e. without the polyurethane elastomer toughener of synthesis, prepares pure PHA thin
Film, as the contrast reference of test result.
(2) mixture solution that step 1 mix homogeneously obtains is cast in mould, after solvent at room temperature volatilization, at 50 DEG C
At a temperature of be vacuum dried 12h, obtain laminated film.
Described PHA powder is biodegradable polyesters PHA powder, for 3-hydroxybutyrate and the 4-hydroxyl of feature of enbrittling
Base butanoic acid copolymer (P (3,4) HB), wherein 4HB molar content is 3.5%.
Polyurethane elastomer (the linear polyurethane bullet of toughness reinforcing Biopolvester PHA of the different hard segment contents of described synthesis
Gonosome toughener) it is degradation material, its soft section is polycaprolactone diols (PCL), and hard section consists of isophorone two isocyanide
Acid esters (IPDI) and 1,4-butanediol (BD).
The present embodiment composite extension test mechanical performance data result such as Fig. 3；Wherein abscissa is percentage elongation；Vertical seat
It is designated as intensity.Composite extension test mechanical performance data table such as Fig. 4；Before and after Fig. 5 is embodiment of the present invention toughening thin film
Section compares SEM photograph；Fig. 6 is the configuration of surface SEM photograph in the embodiment of the present invention before and after laminated film P (3,4) HB-5 degraded
Sheet.
Embodiment 3:
The preparation method of the linear polyurethane elastic body toughening agent of a kind of toughness reinforcing Biopolvester PHA, comprises the steps: pre-
Surely the hard segment content 60% of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA is synthesized, according to recipe calculation formula
The most dried polycaprolactone diols of accurate measurement (PCL, molecular weight 3000) 10g and BDO (BD) 3.6858g with
Isophorone diisocyanate (IPDI) 11.3142g joins in there-necked flask together, uses logical N2Mode completely cuts off air, uses
The method of oil bath heating is heated to 70 DEG C, magnetic agitation, after reaction 2.5h, reactant liquor is proceeded to mould, puts into vacuum drying oven and exist
Carry out chain extension, deaeration at a temperature of 110 DEG C, take out after solidification 18h, obtain the linear polyurethane elastomer that hard segment content is 60%
Toughener；Described recipe calculation formula is as follows:
WIPDI/MIPDI=WPCL/MPCL+WBD/MBD,
Polycaprolactone diols in described step, its molecular weight is 3000；Described dry polycaprolactone diols, passes through
Vacuum drying oven is dried, oven temperature 60 DEG C, drying time 36h.
In described step, hard segment content is the linear polyurethane elastic body toughening agent of 60%, its total NCO and total hydroxyl
Mol ratio NCO:OH=1:1 of base.This formula is different from the spy of a certain feed molar ratio excess in the synthesis of general polyurethane
Levy, by first determining hard segment content, related raw material consumption proportion can be calculated.
W in stepIPDI, WPCL, WBDIt is respectively isophorone diisocyanate, polycaprolactone diols and BDO
Quality；MIPDI, MPCL, MBDIt is respectively isophorone diisocyanate, polycaprolactone diols and mole matter of 1,4-butanediol
Amount, it is respectively 222.29g/mol, 3000g/mol and 90.12g/mol.
Using chemical equation such as Fig. 1 of one-step synthesis method PU, the line style of preparation-obtained toughness reinforcing Biopolvester PHA is gathered
Urethane elastic body toughening agent；Its structural formula is:
；
Wherein n represents the degree of polymerization of polycaprolactone diols (PCL) raw material, and n is between 10～30.Polymerization degree n is according to institute
Depending on the molecular weight of the polycaprolactone diols (PCL) selected, owing to PCL molecular weight is 3000, therefore n is 30.Described increasing
The linear polyurethane elastic body toughening agent of tough Biopolvester PHA is line style degradation material.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA, the steps include:
(1) the linear polyurethane elastic body toughening agent of the toughness reinforcing Biopolvester PHA prepared is weighed 0.05g, 0.1g,
0.2g, 0.3g respectively with 0.95g, 0.9g, 0.8g, 0.7gPHA powder mixes, then mixture is dissolved in 40mL chloroform, super
After sonication 10min, it is placed on shaking table mixing 24h at a temperature of 30 DEG C, is allowed to mix homogeneously；
One contrast reference test is set simultaneously, i.e. without the polyurethane elastomer toughener of synthesis, prepares pure PHA thin
Film, as the contrast reference of test result.
(2) mixture solution that step 1 mix homogeneously obtains is cast in mould, after solvent at room temperature volatilization, at 40 DEG C
At a temperature of be vacuum dried 24h, obtain laminated film.
Described PHA powder is biodegradable polyesters PHA powder, for 3-hydroxybutyrate and the 3-hydroxyl of feature of enbrittling
The copolymer (PHBV) of base valeric acid, wherein (3HV content is 5%).
Polyurethane elastomer (the linear polyurethane bullet of toughness reinforcing Biopolvester PHA of the different hard segment contents of described synthesis
Gonosome toughener) it is degradation material, its soft section is polycaprolactone diols (PCL), and hard section consists of isophorone two isocyanide
Acid esters (IPDI) and 1,4-butanediol (BD).
Embodiment 4:
The preparation method of the linear polyurethane elastic body toughening agent of a kind of toughness reinforcing Biopolvester PHA, comprises the steps: pre-
Surely the hard segment content 50% of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA is synthesized, according to recipe calculation formula
The most dried polycaprolactone diols of accurate measurement (PCL, molecular weight 3000) 10g and BDO (BD) 6.3128g with
Isophorone diisocyanate (IPDI) 16.3127g joins in there-necked flask together, uses logical N2Mode completely cuts off air, uses
The method of oil bath heating is heated to 75 DEG C, magnetic agitation, after reaction 2h, reactant liquor is proceeded to mould, puts into vacuum drying oven 115
Carry out chain extension, deaeration at a temperature of DEG C, take out after solidification 24h, obtain the linear polyurethane elastomer that hard segment content is 50% and increase
Tough dose；Described recipe calculation formula is as follows:
WIPDI/MIPDI=WPCL/MPCL+WBD/MBD,
Polycaprolactone diols in described step, its molecular weight is 3000；Described dry polycaprolactone diols, passes through
Vacuum drying oven is dried, baking temperature 60 DEG C, drying time 24h.
In described step, hard segment content is the linear polyurethane elastic body toughening agent of 50%, its total NCO and total hydroxyl
Mol ratio NCO:OH=1:1 of base.This formula is different from the spy of a certain feed molar ratio excess in the synthesis of general polyurethane
Levy, by first determining hard segment content, related raw material consumption proportion can be calculated.
W in stepIPDI, WPCL, WBDIt is respectively isophorone diisocyanate, polycaprolactone diols and BDO
Quality；MIPDI, MPCL, MBDIt is respectively isophorone diisocyanate, polycaprolactone diols and mole matter of 1,4-butanediol
Amount, it is respectively 222.29g/mol, 3000g/mol and 90.12g/mol.
Using chemical equation such as Fig. 1 of one-step synthesis method PU, the line style of preparation-obtained toughness reinforcing Biopolvester PHA is gathered
Urethane elastic body toughening agent；Its structural formula is:
；
Wherein n represents the degree of polymerization of polycaprolactone diols (PCL) raw material, and n is between 10～30.Polymerization degree n is according to institute
Depending on the molecular weight of the polycaprolactone diols (PCL) selected, owing to PCL molecular weight is 3000, therefore n is 30.Described increasing
The linear polyurethane elastic body toughening agent of tough Biopolvester PHA is line style degradation material.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA, the steps include:
(1) the linear polyurethane elastic body toughening agent of the toughness reinforcing Biopolvester PHA prepared is weighed 0.05g, 0.1g,
0.2g, 0.3g respectively with 0.95g, 0.9g, 0.8g, 0.7gPHA powder mixes, then mixture is dissolved in 40mL chloroform, super
After sonication 8min, it is placed on shaking table mixing 18h at a temperature of 35 DEG C, is allowed to mix homogeneously；
One contrast reference test is set simultaneously, i.e. without the polyurethane elastomer toughener of synthesis, prepares pure PHA thin
Film, as the contrast reference of test result.
(2) mixture solution that step 1 mix homogeneously obtains is cast in mould, after solvent at room temperature volatilization, at 40 DEG C
At a temperature of be vacuum dried 24h, obtain laminated film.
Described PHA powder is biodegradable polyesters PHA powder, for the poly 3-hydroxy butyrate of feature of enbrittling
(PHB)。
Polyurethane elastomer (the linear polyurethane bullet of toughness reinforcing Biopolvester PHA of the different hard segment contents of described synthesis
Gonosome toughener) it is degradation material, its soft section is polycaprolactone diols (PCL), and hard section consists of isophorone two isocyanide
Acid esters (IPDI) and 1,4-butanediol (BD).
Embodiment 5:
The preparation method of the linear polyurethane elastic body toughening agent of a kind of toughness reinforcing Biopolvester PHA, comprises the steps: pre-
Surely the hard segment content 55% of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA is synthesized, according to recipe calculation formula
The most dried polycaprolactone diols of accurate measurement (PCL, molecular weight 1000) 10g and BDO (BD) 2.8858g with
Isophorone diisocyanate (IPDI) 9.3383g joins in there-necked flask together, uses evacuation isolation air, uses oil bath
The method of heating is heated to 80 DEG C, magnetic agitation, after reaction 3h, reactant liquor is proceeded to mould, puts into vacuum drying oven at 110 DEG C
At a temperature of carry out chain extension, deaeration, take out after solidification 24h, obtain the linear polyurethane elastic body toughening agent that hard segment content is 55%；
Described recipe calculation formula is as follows:
WIPDI/MIPDI=WPCL/MPCL+WBD/MBD,
Polycaprolactone diols in described step, its molecular weight is 1000；Described dry polycaprolactone diols, passes through
Vacuum drying oven is dried, baking temperature 50 DEG C, drying time 24h.
In described step, hard segment content is the linear polyurethane elastic body toughening agent of 55%, its total NCO and total hydroxyl
Mol ratio NCO:OH=1:1 of base.This formula is different from the spy of a certain feed molar ratio excess in the synthesis of general polyurethane
Levy, by first determining hard segment content, related raw material consumption proportion can be calculated.
W in stepIPDI, WPCL, WBDIt is respectively isophorone diisocyanate, polycaprolactone diols and BDO
Quality；MIPDI, MPCL, MBDIt is respectively isophorone diisocyanate, polycaprolactone diols and mole matter of 1,4-butanediol
Amount, it is respectively 222.29g/mol, 1000g/mol and 90.12g/mol.
Using chemical equation such as Fig. 1 of one-step synthesis method PU, the line style of preparation-obtained toughness reinforcing Biopolvester PHA is gathered
Urethane elastic body toughening agent；Its structural formula is:
；
Wherein n represents the degree of polymerization of polycaprolactone diols (PCL) raw material, and n is between 10～30.Polymerization degree n is according to institute
Depending on the molecular weight of the polycaprolactone diols (PCL) selected, owing to PCL molecular weight is 1000, therefore n is 10.Described increasing
The linear polyurethane elastic body toughening agent of tough Biopolvester PHA is line style degradation material.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA, the steps include:
(1) the linear polyurethane elastic body toughening agent of the toughness reinforcing Biopolvester PHA prepared is weighed 0.05g, 0.1g,
0.2g, 0.3g respectively with 0.95g, 0.9g, 0.8g, 0.7gPHA powder mixes, then mixture is dissolved in 45mL chloroform, super
After sonication 5min, it is placed on shaking table mixing 12h at a temperature of 30 DEG C, is allowed to mix homogeneously；
One contrast reference test is set simultaneously, i.e. without the polyurethane elastomer toughener of synthesis, prepares pure PHA thin
Film, as the contrast reference of test result.
(2) mixture solution that step 1 mix homogeneously obtains is cast in mould, after solvent at room temperature volatilization, at 35 DEG C
At a temperature of be vacuum dried 24h, obtain laminated film.
Described PHA powder is biodegradable polyesters PHA powder, for 3-hydroxybutyrate and the 4-hydroxyl of feature of enbrittling
Base butanoic acid copolymer (P (3,4) HB), wherein 4HB molar content is 5%.
Polyurethane elastomer (the linear polyurethane bullet of toughness reinforcing Biopolvester PHA of the different hard segment contents of described synthesis
Gonosome toughener) it is degradation material, its soft section is polycaprolactone diols (PCL), and hard section consists of isophorone two isocyanide
Acid esters (IPDI) and 1,4-butanediol (BD).
Claims (8)
1. a preparation method for the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA, comprises the steps:
According to the hard segment content of the linear polyurethane elastic body toughening agent synthesizing toughness reinforcing Biopolvester PHA, according to formula, accurately count
Measure the most dried polycaprolactone diols, BDO and join there-necked flask together with isophorone diisocyanate
In, use evacuation or logical N2Mode completely cuts off air, is heated to 60～80 DEG C with oil bath, magnetic agitation, after reaction 2～3h,
Reactant liquor is proceeded to mould, puts into after vacuum drying oven carries out chain extension, deaeration, solidification 12～24h at a temperature of 100～125 DEG C
Taking out, obtain the linear polyurethane elastic body toughening agent of the toughness reinforcing Biopolvester PHA that hard segment content is 45%～60%, it is the most different
Cyanic acid ester group and mol ratio NCO:OH=1:1 of total hydroxyl；W in described stepIPDI, WPCL, WBDIt is respectively isophorone two isocyanide
Acid esters, polycaprolactone diols and the quality of 1,4-butanediol；MIPDI, MPCL, MBDIt is respectively isophorone diisocyanate, gathers
Caprolactone dihydroxylic alcohols and the molal weight of BDO, it is respectively 222.29g/mol, 1000～3000g/mol and
90.12g/mol；
Described recipe calculation formula is as follows:
WIPDI/MIPDI=WPCL/MPCL+WBD/MBD,
。
The preparation method of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA the most according to claim 1, its
Being characterised by, polycaprolactone diols in described step, its molecular weight is between 1000～3000；Described dry polycaprolactone
Dihydroxylic alcohols, is dried by vacuum drying oven, baking temperature 50～70 DEG C, drying time 24～48h.
3. obtain toughness reinforcing according to the preparation method of the linear polyurethane elastic body toughening agent of claim 1 toughness reinforcing Biopolvester PHA
The linear polyurethane elastic body toughening agent of Biopolvester PHA.
The linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA the most according to claim 3, its structural formula is:
；
Wherein n represents the degree of polymerization of polycaprolactone diols raw material, and n is between 10～30.
The linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA the most according to claim 4, it is characterised in that
The linear polyurethane elastic body toughening agent of described toughness reinforcing Biopolvester PHA is line style degradation material.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA the most according to claim 4, application is such as
The linear polyurethane elastic body toughening agent of the toughness reinforcing Biopolvester PHA obtained by the preparation method of claim 1-2 is as toughness reinforcing
Agent, for the preparation method of biodegradable polyesters PHA laminated film, the steps include:
(1) linear polyurethane elastic body toughening agent and the PHA powder of the toughness reinforcing Biopolvester PHA prepared are mixed, then
Mixture is dissolved in chloroform, after supersound process 5～10min, be placed on shaking table at a temperature of 25～40 DEG C mix 12～
24h, is allowed to mix homogeneously；
(2) mixture solution that step (1) mix homogeneously obtains is cast in mould, after solvent at room temperature volatilization, 30～50
It is vacuum dried at a temperature of DEG C, obtains laminated film.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA the most according to claim 6, its feature
Being, described biodegradable polyesters is PHA powder, including the poly 3-hydroxy butyrate of feature of enbrittling, 3-hydroxybutyrate
With 4 hydroxybutyric acid copolymer, or 3-hydroxybutyrate and the copolymer of 3-hydroxypentanoic acid.
The application of the linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA the most according to claim 6, its feature
Being, the linear polyurethane elastic body toughening agent of described toughness reinforcing Biopolvester PHA and the mixing of PHA powder, PHA/PU mass ratio is
70-95:5-30。
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Application publication date: 20141105 Assignee: Suzhou Anhongtai New Material Co., Ltd. Assignor: Nanjing Forestry University Contract record no.: 2018320000361 Denomination of invention: Linear polyurethane elastomer toughener toughening biopolyester PHA, and preparation method and application thereof Granted publication date: 20161102 License type: Common License Record date: 20181129 |
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Application publication date: 20141105 Assignee: Reliance Environmental Technology (Suzhou) Co., Ltd. Assignor: Nanjing Forestry University Contract record no.: 2019320000111 Denomination of invention: Linear polyurethane elastomer toughener toughening biopolyester PHA, and preparation method and application thereof Granted publication date: 20161102 License type: Common License Record date: 20190423 |
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