CN103819621B - A kind of preparation method of methylene-succinic acid class copolyesters of macromolecular network structure - Google Patents
A kind of preparation method of methylene-succinic acid class copolyesters of macromolecular network structure Download PDFInfo
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- CN103819621B CN103819621B CN201410034095.9A CN201410034095A CN103819621B CN 103819621 B CN103819621 B CN 103819621B CN 201410034095 A CN201410034095 A CN 201410034095A CN 103819621 B CN103819621 B CN 103819621B
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- methylene
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 25
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 25
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 22
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 150000003384 small molecules Chemical class 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000003756 stirring Methods 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- -1 polybutylene Polymers 0.000 description 3
- 229920001748 polybutylene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a kind of preparation method of methylene-succinic acid class copolyesters of macromolecular network structure, the method comprises: component a, components b and amount of component b are reacted under esterifying catalyst effect, component a is dimethyl itaconate, components b is 1,4-butyleneglycol, amount of component b is at least one in the acid anhydrides of aromatic acid, the ester of aromatic acid, aromatic acid.By random copolymerization, aromatic series segment is incorporated in methylene-succinic acid polyester segment and goes, then add crosslinking styrene and be cross-linked under the effect of initiator benzoyl peroxide (BPO), obtain the polyester of macromolecular network structure.This approach improve mechanical property and the thermodynamic property of methylene-succinic acid kind polyester; Synthesis technique is simple, processing ease, and gained polyester has certain biodegradability.
Description
Technical field
The invention belongs to the method field utilizing condensation methods to prepare copolyesters, be specifically related to a kind of preparation method of methylene-succinic acid class copolyesters of macromolecular network structure.
Background technology
20th century synthesized polymer material appearance and fast development significantly improve the life of the mankind, but a large amount of plastic refuse also result in serious environmental pollution, in recent years along with the enhancing of mankind's environmental consciousness, the research and development of degradable high polymer material more and more cause the great attention of people.
The microbial process that Biodegradable polymer material can exist at natures such as bacterium, fungi, algae issues biochemical reaction and generates carbonic acid gas and water, thus returns in nature, as a kind of ep-type material, has caused showing great attention to of people.Aliphatic polyester is one of Biodegradable polymer material, day by day receive publicity because it has the advantage of unique biological degradability, biocompatibility and Bioabsorbable, but poor thermostability and mechanical property and higher production cost constrain it further develops, though aromatic polyester does not have biological degradability, there is excellent mechanical property and thermostability.Therefore, since the nineties in 20th century, the aliphatic-aromatic copolyester that the degradability that preparation has an aliphatic polyester has again a thermostability of aromatic polyester becomes a focus of research.
Methylene-succinic acid and derivative thereof be a kind of have development potentiality biomass industrial chemicals, its raw material methylene-succinic acid can be obtained through fermentation by corn or potato starch, and under Natural compost condition, final degradable is CO
2and H
2o, abundance and renewable, is truly come from nature, is attributed to natural biomass chemical materials.Mostly resistance toheat is poor for the aliphatic polyester of methylene-succinic acid synthesis, and heat decomposition temperature is on the low side, and mechanical property is poor, thus can not get applying widely.
In recent years, biomass chemical materials methylene-succinic acid and derivative thereof become the focus of research both at home and abroad.Patent (CN03112046.6, CN201010617061.4, CN201010617067.1) discloses the application of methylene-succinic acid in multiple field.Can recognize from these patent specifications, methylene-succinic acid tool in water technology, high strength glass fiber reinforced plastic and pesticide intermediate, tackiness agent, scale remover and medicine and other fields has been widely used, oil recovery business abroad in addition, methylene-succinic acid, as the dystectic intermediate of one, has been widely used in the decomposed solution of deep-well oil-extraction.But the research in high molecular polymerization of methylene-succinic acid and derivative thereof rarely has report.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned methylene-succinic acid kind polyester thermomechanical property deficiency, provide a kind of technique simple, the preparation method of the methylene-succinic acid class copolyesters of the macromolecular network structure of processing ease, the copolyesters utilizing technical solution of the present invention to prepare is present in whole molecule with the segment form of random copolymerization, upset the regularity of molecular chain, crystallizing power is reduced, defines macromolecular reticulated structure, therefore its thermostability is significantly improved.
For achieving the above object, the present invention is achieved by the following technical solutions:
A preparation method for the methylene-succinic acid class copolyesters of macromolecular network structure, it comprises the following steps:
1): by component a, components b, amount of component b mixing, add to carry out at esterifying catalyst is warming up to 150 ~ 190 DEG C under nitrogen protection synthesis under normal pressure 2 ~ 5 hours estrodur performed polymer, described component a is dimethyl itaconate, described components b is 1,4-butyleneglycol, described amount of component b is at least one of aromatic acid, the ester of aromatic acid, the acid anhydrides of aromatic acid;
2): described estrodur performed polymer is decompressed to 50Pa, and carry out polycondensation at being warming up to 180 ~ 230 DEG C and slough small molecules in 2 ~ 6 hours, obtain copolyesters;
3): add crosslinking styrene to described copolyesters, in 80 ~ 120 DEG C of crosslinking reaction 0.5 ~ 2h under the effect of initiator benzoyl peroxide, cancellated methylene-succinic acid class copolyesters PBTI is obtained
s.
To the further improvement of technique scheme, in described step 1), the molar ratio proportion optimization of amount of component b integral molar quantity and component a molar weight is 1:9 ~ 9:1.
To the further improvement of technique scheme, in described step 1), the molar weight sum of component a and c and the molar weight proportions of b are 1:1 ~ 1:1.5.
To the further improvement of technique scheme, in described step 1), esterifying catalyst is at least one in tin protochloride, antimonous oxide, magnesium acetate, cerous sulfate, cerous nitrate, tetrabutyl titanate.
To the further improvement of technique scheme, in described step 1), esterifying catalyst consumption is 0.1 ~ 3% of copolymerization system integral molar quantity.
To the further improvement of technique scheme, in described step 3), linking agent is vinylbenzene.
To the further improvement of technique scheme, described vinylbenzene consumption is 0.25 ~ 1 times of copolymerization system integral molar quantity.
To the further improvement of technique scheme, in described step 3), initiator is benzoyl peroxide.
To the further improvement of technique scheme, the mole dosage of described benzoyl peroxide is 0.2% of dimethyl itaconate molar weight.
Compared with prior art, advantage of the present invention and beneficial effect are: the present invention adopts at least one in the acid anhydrides of the ester of aromatic acid, aromatic acid, aromatic acid and dimethyl itaconate, 1,4-butyleneglycol is copolymerization system, transesterify melt phase polycondensation technique is utilized to synthesize methylene-succinic acid class copolyesters, pass through random copolymerization, aromatic series segment is incorporated in methylene-succinic acid polyester segment, finally add crosslinking styrene crosslinked under the effect of initiator benzoyl peroxide (BPO), obtain the polyester of macromolecular network structure.This approach improve mechanical property and the thermodynamic property of methylene-succinic acid kind polyester; Synthesis technique is simple, processing ease, and has certain biodegradability.
Accompanying drawing explanation
Fig. 1 is the PBTI that the present invention obtains
sthe 1H-NMR spectrogram of-3 copolyesters.
Fig. 2 is the PBTI that the present invention obtains
sthe FT-IR spectrogram of-3 copolyesters.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is further described in detail.
Embodiment 1:
The preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure described in the present embodiment comprises the following steps:
1, by mol ratio be terephthalic acid (0.02mol) and the dimethyl itaconate (0.18mol) and 1 of 1:9,4-butyleneglycol (0.2mol) is placed in 100ml flask, add esterifying catalyst tetrabutyl titanate, its add-on is 0.1% of copolymerization system integral molar quantity.Connect water trap, thermometer and agitator, be warming up under nitrogen protection 150 DEG C and violent stirring reaction 2 ~ 5 hours, when no longer include in water trap water generate time the prepolymerization reaction stage terminate, obtain estrodur performed polymer.
2, product polyester performed polymer step 1 obtained is warming up to 180 DEG C, is decompressed to 50Pa and carries out polycondensation, and stirring reaction sloughs small molecules in 2 hours, obtains copolyesters (polybutylene terephthalate-co-methylene-succinic acid butanediol ester, PBTI).
3, cool in the copolyesters in backward reaction unit and add crosslinking styrene (ST) and initiator benzoyl peroxide (BPO), wherein vinylbenzene add that molar weight is copolymerization system integral molar quantity 25%, benzoyl peroxide add that molar weight is dimethyl itaconate molar weight 0.2%.And at 80 DEG C, react 0.5h, the methylene-succinic acid class copolyesters PBTI of macromolecular network structure
s-1.
Embodiment 2:
The preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure described in the present embodiment comprises the following steps:
1, by mol ratio be terephthalate (0.18mol) and the dimethyl itaconate (0.02mol) and 1 of 9:1,4-butyleneglycol (0.3mol) is placed in 100ml flask, add esterifying catalyst tetrabutyl titanate, its add-on is 3% of copolymerization system integral molar quantity.Connect water trap, thermometer and agitator, be warming up under nitrogen protection 190 DEG C and violent stirring reaction 2 ~ 5 hours, when no longer include in water trap water generate time the prepolymerization reaction stage terminate, obtain estrodur performed polymer.
2, product polyester performed polymer step 1 obtained is warming up to 230 DEG C, is decompressed to 50Pa and carries out polycondensation, and stirring reaction sloughs small molecules in 6 hours, obtains copolyesters.
3, cool in backward reaction unit and add crosslinking styrene and initiator benzoyl peroxide, wherein vinylbenzene add that molar weight is copolymerization system integral molar quantity 100%, benzoyl peroxide add that molar weight is dimethyl itaconate molar weight 0.2%.And at 80 DEG C, react 2h, the methylene-succinic acid class copolyesters PBTI of macromolecular network structure
s-2.
Embodiment 3:
The preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure described in the present embodiment comprises the following steps:
1, by mol ratio be terephthalic acid (0.06mol) and the dimethyl itaconate (0.14mol) and 1 of 3:7,4-butyleneglycol (0.26mol) is placed in 100ml flask, add esterifying catalyst antimonous oxide, its add-on is 1% of copolymerization system integral molar quantity.Connect water trap, thermometer and agitator, be warming up under nitrogen protection 160 DEG C and violent stirring reaction 2 ~ 5 hours, when no longer include in water trap water generate time the prepolymerization reaction stage terminate, obtain estrodur performed polymer.
2, product polyester performed polymer step 1 obtained is warming up to 200 DEG C, is decompressed to 50Pa and carries out polycondensation, and stirring reaction sloughs small molecules in 3 hours, obtains copolyesters.
3, cool in backward reaction unit and add crosslinking styrene and initiator benzoyl peroxide, wherein vinylbenzene add that molar weight is copolymerization system integral molar quantity 50%, benzoyl peroxide add that molar weight is dimethyl itaconate molar weight 0.2%.And at 80 DEG C, react 1h, the methylene-succinic acid class copolyesters PBTI of macromolecular network structure
s-3.
Through the polybutylene terephthalate-co-methylene-succinic acid butanediol ester (PBTI that preparation method of the present invention obtains
s-3) structural formula is as follows:
PBTI copolyesters
1h-NMR spectrogram is shown in Fig. 1.As can be seen from Figure 1,1 of chemical shift δ=8.091 correspondence is positioned at
#peak is 4 proton hydrogen on terephthalic acid phenyl ring; Be positioned at δ=6.317,5.729 correspondences 2
#, 3
#peak is=CH
2two proton hydrogen, because double bond the other end substituting group is different, cause proton peak to be coupled splitting point; The peak 10 that place, δ=3.674 is corresponding
#, peak position and peak area thereof are known by inference for-OH proton hydrogen, and the position that on spectrogram, chemical shift is greater than 8 in addition does not go out peak, shows that polyester end is alcohol-OH instead of carboxyl; Place, δ=2.584 corresponding unimodal 12
#, according to peak position, peak shape, peak area can should be 2 protons on the carbon that is connected with carbonyl carbon with double key carbon in methylene-succinic acid.
Fig. 2 is the FT-IR spectrogram of copolyesters, 3679.58cm
-1the broad band at place is that polyester end dissociates the stretching vibration absorption peak of-OH; 1640.54cm
-1the spike at place is double bond stretching vibration peak, 2960.98cm
-1place is=the stretching vibration absorption peak of C-H, 874.37cm
-1absorption peak be=CH
2out-of-plane deformation vibration, shows there is-C=CH jointly above
2exist; 1714.64cm
-1 strong peak, place isthe stretching vibration absorption peak of-C=O; 1504.30,1455.59,1409.47cm
-1absorption peak show there is benzene ring structure; 729.90cm
-1the spike at place is-(CH in BDO
2)
4-rocking vibration absorption peak.
Fig. 1 and Fig. 2 about
1the spectrogram of H-NMR and FT-IR shows that products therefrom is polybutylene terephthalate-co-methylene-succinic acid butanediol ester.
Embodiment 4:
The preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure described in the present embodiment comprises the following steps:
1, be that the terephthalic anhydride (0.08mol) of 4:6 and dimethyl itaconate (0.12mol) and BDO (0.28mol) are placed in 100ml flask by mol ratio, add esterifying catalyst cerous sulfate, its add-on is 2% of copolymerization system integral molar quantity.Connect water trap, thermometer and agitator, be warming up under nitrogen protection 170 DEG C and violent stirring reaction 2 ~ 5 hours, when no longer include in water trap water generate time the prepolymerization reaction stage terminate, obtain estrodur performed polymer.
2, product polyester performed polymer step 1 obtained is warming up to 210 DEG C, is decompressed to 50Pa and carries out polycondensation, and stirring reaction sloughs small molecules in 4 hours, obtains copolyesters.
3, cool in backward reaction unit and add crosslinking styrene and initiator benzoyl peroxide, wherein vinylbenzene add that molar weight is copolymerization system integral molar quantity 60%, benzoyl peroxide add that molar weight is dimethyl itaconate molar weight 0.2%.And at 80 DEG C, react 1.5h, the methylene-succinic acid class copolyesters PBTI of macromolecular network structure
s-4.
Embodiment 5:
The preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure described in the present embodiment comprises the following steps:
1, be that the terephthalic acid (0.1mol) of 1:1 and dimethyl itaconate (0.1mol) and BDO (0.25mol) are placed in 100ml flask by mol ratio, add esterifying catalyst tin protochloride, its add-on is 0.5% of copolymerization system integral molar quantity.Connect water trap, thermometer and agitator, be warming up under nitrogen protection 180 DEG C and violent stirring reaction 2 ~ 5 hours, when no longer include in water trap water generate time the prepolymerization reaction stage terminate, obtain estrodur performed polymer.
2, product polyester performed polymer step 1 obtained is warming up to 220 DEG C, is decompressed to 50Pa and carries out polycondensation, and stirring reaction sloughs small molecules in 5 hours, obtains copolyesters.
3, cool in backward reaction unit and add crosslinking styrene and initiator benzoyl peroxide, wherein vinylbenzene add that molar weight is copolymerization system integral molar quantity 50%, benzoyl peroxide add that molar weight is dimethyl itaconate molar weight 0.2%.And at 80 DEG C, react 1h, the methylene-succinic acid class copolyesters PBTI of macromolecular network structure
s-5.
Embodiment 6:
The preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure described in the present embodiment comprises the following steps:
1, by mol ratio be terephthalate (0.14mol) and the dimethyl itaconate (0.06mol) and 1 of 7:3,4-butyleneglycol (0.24mol) is placed in 100ml flask, add esterifying catalyst magnesium acetate, its add-on is 0.8% of copolymerization system integral molar quantity.Connect water trap, thermometer and agitator, be warming up under nitrogen protection 160 DEG C and violent stirring reaction 2 ~ 5 hours, when no longer include in water trap water generate time the prepolymerization reaction stage terminate, obtain estrodur performed polymer.
2, product polyester performed polymer step 1 obtained is warming up to 200 DEG C, is decompressed to 50Pa and carries out polycondensation, and stirring reaction sloughs small molecules in 4 hours, obtains copolyesters.
3, cool in backward reaction unit and add crosslinking styrene and initiator benzoyl peroxide, wherein vinylbenzene add that molar weight is copolymerization system integral molar quantity 40%, benzoyl peroxide add that molar weight is dimethyl itaconate molar weight 0.2%.And at 80 DEG C, react 1h, the methylene-succinic acid class copolyesters PBTI of macromolecular network structure
s-6.
Embodiment 7:
The preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure described in the present embodiment comprises the following steps:
1, by mol ratio be terephthalic acid (0.16mol) and the dimethyl itaconate (0.04mol) and 1 of 4:1,4-butyleneglycol (0.3mol) is placed in 100ml flask, add esterifying catalyst tetrabutyl titanate, its add-on is 1.5% of copolymerization system integral molar quantity.Connect water trap, thermometer and agitator, be warming up under nitrogen protection 170 DEG C and violent stirring reaction 2 ~ 5 hours, when no longer include in water trap water generate time the prepolymerization reaction stage terminate, obtain estrodur performed polymer.
2, product polyester performed polymer step 1 obtained is warming up to 220 DEG C, is decompressed to 50Pa and carries out polycondensation, and stirring reaction sloughs small molecules in 3 hours, obtains copolyesters.
3, cool in backward reaction unit and add crosslinking styrene and initiator benzoyl peroxide, wherein vinylbenzene add that molar weight is copolymerization system integral molar quantity 30%, benzoyl peroxide add that molar weight is dimethyl itaconate molar weight 0.2%.And at 80 DEG C, react 1.5h, the methylene-succinic acid class copolyesters PBTI of macromolecular network structure
s-7.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (8)
1. a preparation method for the methylene-succinic acid class copolyesters of macromolecular network structure, it is characterized in that, it comprises the following steps:
1): by component a, components b, amount of component b mixing, add and carry out synthesis under normal pressure 2-5h at esterifying catalyst is warming up to 150-190 DEG C under nitrogen protection and obtain estrodur performed polymer, described component a is dimethyl itaconate, described components b is 1,4-butyleneglycol, described amount of component b is at least one of aromatic acid, the ester of aromatic acid, the acid anhydrides of aromatic acid, and the molar weight sum of described component a and c and the molar weight proportions of b are 1:1-1:1.5;
2): described estrodur performed polymer is decompressed to 50Pa, and carry out polycondensation 2-6h at being warming up to 180-230 DEG C and slough small molecules, obtain copolyesters;
3): add crosslinking styrene to described copolyesters, in 80-120 DEG C crosslinking reaction 0.5-2h under the effect of initiator benzoyl peroxide, cancellated methylene-succinic acid class copolyesters PBTI is obtained
s.
2. prepare the preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure according to claim 1, it is characterized in that, in described step 1), the molar ratio proportioning of amount of component b and component a is 1:9-9:1.
3. according to claim 1 or 2, prepare the preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure, it is characterized in that, in described step 1), esterifying catalyst is at least one in tin protochloride, antimonous oxide, magnesium acetate, cerous sulfate, cerous nitrate, tetrabutyl titanate.
4. prepare the preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure according to claim 3, it is characterized in that, in described step 1), esterifying catalyst consumption is the 0.1-3% of copolymerization system integral molar quantity.
5. prepare the preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure according to claim 1, it is characterized in that, in described step 3), linking agent is vinylbenzene.
6. prepare the preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure according to claim 5, it is characterized in that, described vinylbenzene consumption is 0.25-1 times of copolymerization system integral molar quantity.
7. prepare the preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure according to claim 1, it is characterized in that, in described step 3), initiator is benzoyl peroxide.
8. prepare the preparation method of the methylene-succinic acid class copolyesters of macromolecular network structure according to claim 7, it is characterized in that, the mole dosage of described benzoyl peroxide is 0.2% of dimethyl itaconate molar weight.
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| CN108239267B (en) * | 2016-12-27 | 2021-02-19 | 深圳市虹彩新材料科技有限公司 | Compound for polylactic acid modification and preparation method and application thereof |
| CN109251942A (en) * | 2018-09-17 | 2019-01-22 | 北京化工大学 | A kind of method of lipase-catalyzed synthesis itaconic acid polyester |
| CN115124705A (en) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | Degradable copolyester material and preparation method and application thereof |
| CN114621424B (en) * | 2022-01-07 | 2023-06-13 | 浙江恒逸石化研究院有限公司 | Preparation method of aliphatic-aromatic linear copolyester containing itaconic acid |
| CN116535631B (en) * | 2023-04-17 | 2023-12-01 | 浙江澳宇新材料科技有限公司 | Degradable copolyester hot melt adhesive and preparation method thereof |
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| US7259227B2 (en) * | 2001-11-12 | 2007-08-21 | Uhde Inventa-Fischer Gmbh | Method for continuous production of high-molecular weight polyesters and device for implementation of the method |
| CN102361906A (en) * | 2009-03-25 | 2012-02-22 | 帝斯曼知识产权资产管理有限公司 | Unsaturated polyester |
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| US7259227B2 (en) * | 2001-11-12 | 2007-08-21 | Uhde Inventa-Fischer Gmbh | Method for continuous production of high-molecular weight polyesters and device for implementation of the method |
| CN102361906A (en) * | 2009-03-25 | 2012-02-22 | 帝斯曼知识产权资产管理有限公司 | Unsaturated polyester |
| CN102361907A (en) * | 2009-03-25 | 2012-02-22 | 帝斯曼知识产权资产管理有限公司 | Unsaturated polyester resin composition |
| CN102361905A (en) * | 2009-03-25 | 2012-02-22 | 帝斯曼知识产权资产管理有限公司 | Unsaturated polyester resin |
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