CN102863626B - Biomass modified polymer and preparation method and application thereof - Google Patents

Biomass modified polymer and preparation method and application thereof Download PDF

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CN102863626B
CN102863626B CN201110188429.4A CN201110188429A CN102863626B CN 102863626 B CN102863626 B CN 102863626B CN 201110188429 A CN201110188429 A CN 201110188429A CN 102863626 B CN102863626 B CN 102863626B
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starch
coupling agent
pet
diisocyanate
biomass
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CN102863626A (en
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王鑫
黎元生
乔凯
金平
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a biomass modified polymer, a preparation method and application of the biomass modified polymer. Modified PET (Polyethylene Glycol Terephthalate) and starch as raw materials and dimethyl sulfoxide as a solvent are polymerized to obtain the biomass modified polymer in the presence of a coupling agent-diisocyanate, the reaction temperature is 90 to 120 DEG. C and the reaction time is 3 to 24h; and the modified PET is a polymerization product of terephthalic acid or polyethylene terephthalate and ethylene glycol or long-chain diol or lactone, and the mole ratio of terephthalic acid or polyethylene terephthalate to diol is 1 to 1. The biomass modified polymer is high in intrinsic viscosity, free from crosslinking, and liable to process, and has biodegradability; and the preparation method is simple, the biomass modified polymer can be quickly polymerized, and the cost is low, so that the biomass modified polymer as a high polymer material is suitable for industrial application.

Description

A kind of biomass modified polymkeric substance and its preparation method and application
Technical field
The present invention relates to a kind of biomass modified polymkeric substance and its preparation method and application.
Background technology
Polyethylene terephthalate (PET) is a kind of commodity polymer material of excellent property, is widely used in every field, as the production of POLYESTER YARNS, and the manufacture of film and beverage bottle, but PET is very slow at occurring in nature degradation speed, to environment.People had carried out broad research to biodegradable material in recent years.As biomass resource and synthetic polymer are prepared into biodegradable shaped material by blend, carrying out of this research, has opened up a new way for solving the pollution of waste plastic.The biomass such as starch, Mierocrystalline cellulose, as a class polysaccharide-based composite high-molecular, have advantages of degradable, renewable, cheap and wide material sources, are more and more subject to people and pay close attention to.
Because hydrophilic starch and hydrophobicity polyester are inconsistent, the water tolerance of simple physical blending system and mechanical property are improved and are unsatisfactory, can not fundamentally solve the problem of PET difficult degradation.Utilize starch and cellulose chemistry modified PET can give starch/PET, Mierocrystalline cellulose/PET system is applied widely.
US3950282 and US3386932 disclose respectively a kind of preparation method who contains Mierocrystalline cellulose segmented copolymer.These class methods first obtain cellulose degradation the Mierocrystalline cellulose of short chain, then by method protection hydroxyls such as esterification, acidylates, then acidifying obtains containing reductibility terminal hydroxy group, with vulcabond and polyester, carries out coupling, and last Deprotection obtains target multipolymer.The polymkeric substance that this method makes is successively through acidolysis-steps such as protection-coupling-deprotection, and technical process is longer, and cost is higher.
Lee etc. have reported with amylose starch and PET coupling and have prepared starch-containing segment block polymer in < < PolymerChemistry Edition > > the 20th 4 phase of volume P997-1009 " Amylose – polyester block copolymers ".The amylose starch using is without degraded directly by hydroxyl protection, then acidifying obtains containing reductibility terminal hydroxy group, then carries out successively linked reaction and deprotection, obtains the polymkeric substance that intrinsic viscosity is 0.53 dl/g.Polymer viscosity that this method obtains is lower can not meet materials processing performance requriements completely, and the hydroxyl in starch still needs protection and deprotection process, operates more numerous and diverse.
Starch, cellulosic poly-hydroxy structures shape its there is higher reactive behavior; under high temperature, carry out coupling with polyester and crosslinking reaction easily occurs form also undissolved product of neither melting, normally used method is that the hydroxyl on sugar ring is carried out to selective protection for this reason.The fusing point of PET is very high (270-280 ℃) generally, this just makes the biomass such as starch, Mierocrystalline cellulose be difficult to directly by the method for melt polymerization, obtain the polymer materials of high intrinsic viscosity, and at a lower temperature directly by the direct and PET polymerization by solution of the biomass such as starch, Mierocrystalline cellulose, not only polymerization is slow, efficiency is low, and the polymer intrinsic viscosity ([η] <0.6 dl/g) on the low side of preparation is difficult to reach the requirement of materials processing performance.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of biomass modified polymkeric substance and its preparation method and application.This biomass modified polymkeric substance not only intrinsic viscosity high, be not cross-linked, be easy to processing, there is biodegradability, and preparation method is simple, can rapid polymerization, cost is low, be suitable for carrying out industrial application as macromolecular material.
A biomass modified polymkeric substance, has following structure:
Figure 261847DEST_PATH_IMAGE002
Wherein, St representative structure is
Figure 68260DEST_PATH_IMAGE004
starch glucose ring segment, the polymerization degree that x is starch; MPET is represented as modified PET segment; R represents hydrocarbyl portion in chainextender vulcabond, and described modified PET segmented structure is as follows:
Figure 822590DEST_PATH_IMAGE006
Or
Figure 621918DEST_PATH_IMAGE008
wherein P, T are respectively the hydrocarbyl portion of long chain diol and lactone, and m, n be respectively>=1 integer, in this multipolymer, the quality percentage composition of starch is 5 ~ 60%, intrinsic viscosity is 0.6-1.2 dl/g.
A kind of preparation method of biomass modified polymkeric substance: using modified PET and starch as raw material, take dimethyl sulfoxide (DMSO) as solvent, under the existence of coupling agent vulcabond, carry out polyreaction and make biomass modified polymkeric substance, temperature of reaction is 90 ~ 120 ℃, reaction times 3 ~ 24h, described modified PET is the polymerisate of terephthalic acid or ester and ethylene glycol and long chain diol or lactone, and the mol ratio of terephthalic acid or ester and dibasic alcohol is 1:1.
Starch material described in the inventive method according to floristics comprise W-Gum, potato starch, Starch rice, wheat starch, sweet potato starch etc. any and combination, according to constructional feature comprise amylopectin, amylose starch, Zulkovsky starch and modified starch etc. any and combination.The mass ratio of starch material and modified PET is 1:1 ~ 1:20.
Coupling agent vulcabond described in the inventive method comprises any of hexamethylene diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, preferably hexamethylene diisocyanate.The mol ratio of coupling agent vulcabond and modified PET is 2:1.
Long chain diol described in the inventive method comprises that general structure is HO (CH 2) noH(n=6 ~ 10) aliphatic dihydroxy alcohol, polyoxyethylene glycol HO (CH 2cH 2o) noH(m=2 ~ 20) and polypropylene glycol HO (CH 2cH 2cH 2o) noH(m=2 ~ 10); Conventional long chain diol has one or more of 1,6-hexylene glycol, decamethylene-glycol, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, cetomacrogol 1000, polypropylene glycol 500.Described lactone comprises that gamma-butyrolactone, 6-caprolactone etc. can open loop form any one lactone of long-chain terminal hydroxy group, preferably 6-caprolactone.
The biomass modified polymkeric substance of the present invention can be used as the application of fiber (containing non-woven fabrics), all types of plastic goods, wrapping material and sizing agent material.
In order to reach effect of the present invention, avoid producing the problem that prior art occurs, to obtain, there is higher intrinsic viscosity and machinable biomass modified polymkeric substance, the inventive method with long chain diol or lactone modified PET directly and starch by efficiently preparing qualified biomass modified polymkeric substance under solution polymerization cold condition.Specifically, compared with prior art, biomass modified polymkeric substance of the present invention and its preparation method and application tool has the following advantages:
1, the inventive method is used modified PET, has realized and under cold condition, has carried out solution polymerization, prevents from having overcome when starch is crosslinked in prior art polymerization not enough slowly, has improved polymerization efficiency;
2, the biomass modified polymer modification PET of the present invention can carry out polymerization with a plurality of hydroxyls of starch, and the intrinsic viscosity of this polymkeric substance is high, biodegradable, meets processing request, is suitable for applying as degradable macromolecular material;
3, the inventive method technique is simple, adopts direct solution polymerization process to prepare starch conversion polymkeric substance, does not need starch hydroxyl to protect and deprotection processing, has simplified technical process, has reduced energy consumption.
Accompanying drawing explanation
fig. 1 is the embodiment of the present invention 4 1h-NMR spectrogram and the polymer architecture identifying.
Embodiment
Below by embodiment, further illustrate process and the effect of the inventive method, the preparation that wherein embodiment 1-3 is modified PET.
Embodiment 1
The preparation of PET-PEG400: by be the polyoxyethylene glycol (Mw=400) of 1:2:3 in molar ratio, to first rutgers, ethylene glycol, with first rutgers mass percent is respectively to 0.03% esterifying catalyst zinc acetate and 0.05% polycondensation catalyst butyl (tetra) titanate, mix, first under nitrogen atmosphere, 190 ℃ of reaction 4h of temperature, then 260 ℃ of temperature, polycondensation 3h under pressure 100Pa.
Embodiment 2
The preparation of PET-HD: by be the hexylene glycol of 1:10:19 in molar ratio, to first rutgers, ethylene glycol, with first rutgers mass percent is respectively to 0.03% esterifying catalyst zinc acetate and 0.05% polycondensation catalyst butyl (tetra) titanate, mix, first under nitrogen atmosphere, 190 ℃ of reaction 4h of temperature, then 260 ℃ of temperature, polycondensation 3h under pressure 100Pa.
Embodiment 3
The preparation of PET-CAP: by be the 6-caprolactone of 1:10:19 in molar ratio, to first rutgers, ethylene glycol, with first rutgers mass percent is respectively to 0.03% esterifying catalyst zinc acetate and 0.1% polycondensation catalyst antimony acetate, mix, first under nitrogen atmosphere, 170 ℃ of reaction 2h of temperature, then 240 ℃ of temperature, polycondensation 3h under pressure 20Pa.
Embodiment 4
To product in embodiment 1, add 5 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent hexamethylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 5 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET-PEG400 mass ratio are 1:1, to be mixed after, be warming up to 90 ℃, react 24h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 58.7%, and intrinsic viscosity is 0.92 dl/g.
Embodiment 5
To product in embodiment 1, add 10 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent hexamethylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 5 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET-PEG400 mass ratio are 1:9, to be mixed after, be warming up to 90 ℃, react 3h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 12.1%, and intrinsic viscosity is 0.87 dl/g.
Embodiment 6
To product in embodiment 1, add 10 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent hexamethylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 10 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET-PEG400 mass ratio are 1:20, to be mixed after, be warming up to 90 ℃, react 3h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 5.2%, and intrinsic viscosity is 0.74 dl/g.
Embodiment 7
To product in embodiment 2, add 10 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent tolylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 10 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET-HD mass ratio are 1:2, to be mixed after, be warming up to 120 ℃, react 3h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 36.4%, and intrinsic viscosity is 0.65 dl/g.
Embodiment 8
To product in embodiment 2, add 10 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent hexamethylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 10 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET-HD mass ratio are 1:9, to be mixed after, be warming up to 90 ℃, react 24h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 11.2%, and intrinsic viscosity is 1.07 dl/g.
Embodiment 9
To product in embodiment 3, add 10 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent hexamethylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 10 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET-CAP mass ratio are 1:9, to be mixed after, be warming up to 90 ℃, react 24h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 10.6%, and intrinsic viscosity is 1.17 dl/g.
Embodiment 10
To product in embodiment 3, add 10 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent hexamethylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 10 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET-CAP mass ratio are 1:9, to be mixed after, be warming up to 120 ℃, react 5h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 12.4%, and intrinsic viscosity is 1.24 dl/g.
Comparative example 1(compares with embodiment 5)
PET preparation: by be in molar ratio 1:2 to first rutgers, ethylene glycol, with first rutgers mass percent is respectively to 0.03% esterifying catalyst zinc acetate and 0.05% polycondensation catalyst butyl (tetra) titanate, mix, first under nitrogen atmosphere, 190 ℃ of reaction 4h of temperature, then 260 ℃ of temperature, polycondensation 3h under pressure 100Pa.
To above-mentioned middle product, add 10 times of quality to be dried dimethyl sulfoxide (DMSO), at N 2under atmosphere, stir until dissolve at 90 ℃ of temperature, dropwise add coupling agent hexamethylene diisocyanate, polymkeric substance and coupling agent mole number are 1:2, stirring reaction 4h.
Zulkovsky starch is dissolved in to the dry dimethyl sulfoxide (DMSO) of 10 times of quality, at N simultaneously 2under atmosphere, stir until dissolve under temperature 60 C, then above-mentioned reaction solution is slowly added, in mixed solution, starch and PET mass ratio are 1:9, to be mixed after, be warming up to 90 ℃, react 3h.After reaction finishes, the multipolymer obtaining is removed to unreacted starch with water precipitation, put into loft drier in 30 ℃ of vacuum-drying 24h.During products therefrom structure forms, the percentage composition of starch is 5.9%, and intrinsic viscosity is 0.47dl/g.

Claims (7)

1. the preparation method of a biomass modified polymkeric substance, it is characterized in that: using modified PET and starch as raw material, take dimethyl sulfoxide (DMSO) as solvent, under the existence of coupling agent vulcabond, carry out polyreaction and make biomass modified polymkeric substance, temperature of reaction is 90 ~ 120 ℃, reaction times 3 ~ 24h, described modified PET is the polymerisate of terephthalic acid or ester and ethylene glycol and long chain diol or lactone, wherein, the mol ratio of terephthalic acid or ester and dibasic alcohol is 1:1, and what make polymer-modifiedly has a following structure:
Figure 891609DEST_PATH_IMAGE001
Wherein, St representative structure is
Figure 776388DEST_PATH_IMAGE002
starch glucose ring segment, the polymerization degree that x is starch; MPET is represented as modified PET segment; R represents hydrocarbyl portion in chainextender vulcabond, and described modified PET segmented structure is as follows:
Or
Figure 366955DEST_PATH_IMAGE004
wherein, P, T are respectively the hydrocarbyl portion of long chain diol and lactone, and m, n be respectively>=1 integer, in this multipolymer, the quality percentage composition of starch is 5 ~ 60%, intrinsic viscosity is 0.6-1.2 dL/g.
2. method according to claim 1, is characterized in that: starch material comprises one or more mixing in W-Gum, potato starch, Starch rice, wheat starch or sweet potato starch.
3. method according to claim 1, is characterized in that: the mass ratio of starch material and modified PET is 1:1 ~ 1:20.
4. method according to claim 1, is characterized in that: coupling agent vulcabond comprises one or more mixing in hexamethylene diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate or xylylene diisocyanate.
5. method according to claim 1, is characterized in that: coupling agent vulcabond is hexamethylene diisocyanate, and the mol ratio of coupling agent vulcabond and modified PET is 2:1.
6. method according to claim 1, is characterized in that: long chain diol is one or more in 1,6-hexylene glycol, decamethylene-glycol, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, cetomacrogol 1000 or polypropylene glycol 500.
7. method according to claim 1, is characterized in that: lactone is for can open loop forming any one lactone of long-chain terminal hydroxy group.
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CN102007159A (en) * 2008-04-15 2011-04-06 巴斯夫欧洲公司 Method for the continuous production of biodegradable polyesters

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