CN117986487A - Modified polyglycolic acid raw material composition with improved compressive property, modified polyglycolic acid, preparation method and application thereof - Google Patents
Modified polyglycolic acid raw material composition with improved compressive property, modified polyglycolic acid, preparation method and application thereof Download PDFInfo
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- CN117986487A CN117986487A CN202211332608.5A CN202211332608A CN117986487A CN 117986487 A CN117986487 A CN 117986487A CN 202211332608 A CN202211332608 A CN 202211332608A CN 117986487 A CN117986487 A CN 117986487A
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- Prior art keywords
- polyglycolic acid
- groups
- modified polyglycolic
- modified
- compression resistance
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 146
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 142
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000002994 raw material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 36
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- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 12
- 238000007906 compression Methods 0.000 claims description 47
- 230000006835 compression Effects 0.000 claims description 47
- 238000001816 cooling Methods 0.000 claims description 35
- 238000001125 extrusion Methods 0.000 claims description 25
- 239000000155 melt Substances 0.000 claims description 20
- -1 acyl peroxide Chemical class 0.000 claims description 18
- 150000003254 radicals Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 239000003814 drug Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 5
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical class CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
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- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 4
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- NYWXVXOJEFSARE-UHFFFAOYSA-N 2-(3-methylphenyl)benzotriazole Chemical compound CC1=CC=CC(N2N=C3C=CC=CC3=N2)=C1 NYWXVXOJEFSARE-UHFFFAOYSA-N 0.000 claims description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 2
- YBIGQANAFDQTNA-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-ethoxyphenol Chemical compound OC1=CC(OCC)=CC=C1N1N=C2C=CC=CC2=N1 YBIGQANAFDQTNA-UHFFFAOYSA-N 0.000 claims description 2
- HZTYZWICLYUPSX-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-methoxyphenol Chemical compound OC1=CC(OC)=CC=C1N1N=C2C=CC=CC2=N1 HZTYZWICLYUPSX-UHFFFAOYSA-N 0.000 claims description 2
- QNLZWPIRRRXADH-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-propoxyphenol Chemical compound OC1=CC(OCCC)=CC=C1N1N=C2C=CC=CC2=N1 QNLZWPIRRRXADH-UHFFFAOYSA-N 0.000 claims description 2
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- KVWLLOIEGKLBPA-UHFFFAOYSA-N 3,6,9-triethyl-3,6,9-trimethyl-1,2,4,5,7,8-hexaoxonane Chemical compound CCC1(C)OOC(C)(CC)OOC(C)(CC)OO1 KVWLLOIEGKLBPA-UHFFFAOYSA-N 0.000 claims description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- UQAMDAUJTXFNAD-UHFFFAOYSA-N 4-(4,6-dichloro-1,3,5-triazin-2-yl)morpholine Chemical compound ClC1=NC(Cl)=NC(N2CCOCC2)=N1 UQAMDAUJTXFNAD-UHFFFAOYSA-N 0.000 claims description 2
- SGZWJGRZDJCDIM-UHFFFAOYSA-N 4-[4,6-bis(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1C1=NC(C=2C(=CC(O)=CC=2)O)=NC(C=2C(=CC(O)=CC=2)O)=N1 SGZWJGRZDJCDIM-UHFFFAOYSA-N 0.000 claims description 2
- BZSDFBVWSOCWIN-UHFFFAOYSA-N 4-[4-(benzotriazol-2-yl)-3-hydroxyphenoxy]butanoic acid Chemical compound N=1N(N=C2C=1C=CC=C2)C1=C(C=C(OCCCC(=O)O)C=C1)O BZSDFBVWSOCWIN-UHFFFAOYSA-N 0.000 claims description 2
- IEMHIOUNBGZEAG-UHFFFAOYSA-N 4-tert-butyl-2-(5-chlorobenzotriazol-2-yl)phenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 IEMHIOUNBGZEAG-UHFFFAOYSA-N 0.000 claims description 2
- FQTSQICZRGKPEQ-UHFFFAOYSA-N 6-methylheptyl 3-(4-methoxyphenyl)prop-2-enoate Chemical compound COC1=CC=C(C=CC(=O)OCCCCCC(C)C)C=C1 FQTSQICZRGKPEQ-UHFFFAOYSA-N 0.000 claims description 2
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a modified polyglycolic acid raw material composition with improved compressive property, a modified polyglycolic acid, a preparation method and application thereof. The invention relates to a raw material composition of modified polyglycolic acid with improved compressive property, which comprises the following components: 100 parts by mass of polyglycolic acid; 0.5 to 15 parts by mass of compressive property modifier; peroxide 0.01-2 parts by mass; 0-2 parts by mass of processing aid. According to the invention, the compressive property of the PGA is improved by grafting and modifying the PGA through the compressive property modifier, and the toughness of the PGA is not reduced, so that a better technical effect is achieved.
Description
Technical Field
The invention relates to the technical field of polyglycolic acid modification, in particular to a modified polyglycolic acid raw material composition with improved compressive property, modified polyglycolic acid, a preparation method and application thereof.
Background
Polyglycolic acid (PGA), the simplest linear aliphatic polyester, is a typical high crystallinity polymer that is lattice stable and has a relatively high melting point. The PGA has the advantages of excellent biodegradability, high degradation speed, good biocompatibility, good bioresorbability, high mechanical strength (certain indexes are relative to standard engineering plastics) and the like, and is mainly applied to the fields of medical suture lines, drug controlled release carriers, fracture fixing materials, tissue engineering scaffolds, reinforcing materials, oil gas exploitation and the like.
Hydrocarbon production typically requires the use of downhole tools such as temporary plugging balls, bridge plugs, and the like. Temporary plugging balls are mainly divided into two types, namely dissolution type and degradation type. The solubility of the soluble metal temporary plugging ball in the well is uncertain due to the distinct differences of the temperature, mineralization degree, pH value and the like in the well, and the application range of the soluble metal temporary plugging ball is influenced. Compared with the metal temporary plugging balls, the degradation of the degradation type temporary plugging balls (such as PGA temporary plugging balls) is less influenced by salinity or chemicals, and can be applied to clean water and high salinity water fracturing. The temporary plugging ball is made of degradable plastics, can be degraded after being used without collection and recovery, saves cost and has little influence on an oil well. The PGA temporary plugging balls have little change in short-term structural integrity and mechanical properties at room temperature. However, when oil and gas wells above 80 ℃ and especially above 120 ℃ are produced, the crystal structure of PGA is broken by high temperature acceleration, and the compressive properties thereof are low, thereby limiting the application thereof.
The conventional inorganic component reinforcing method (such as fiber reinforcement and inorganic filler reinforcement) causes the density of the PGA temporary plugging balls to be too high, the toughness to be reduced, and the degraded residues have the risk of plugging the oil well construction pump body.
Accordingly, there is a need to provide a new method of modifying PGA to improve its compressive properties.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified polyglycolic acid raw material composition with improved compressive property, modified polyglycolic acid, and a preparation method and application thereof. According to the invention, the compressive property of the PGA is improved by grafting and modifying the PGA through the compressive property modifier, and the toughness of the PGA is not reduced, so that a better technical effect is achieved.
One of the purposes of the invention is to provide a modified polyglycolic acid raw material composition with improved compressive property, which comprises the following components:
100 parts by mass of polyglycolic acid;
0.5 to 15 parts by mass of compressive property modifier; for example, 0.5, 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by mass, and any range consisting of any two of the above values;
0.01 to 2 parts by mass of a free radical initiator; for example, 0.01, 0.1, 0.2, 0.3, 0.5, 0.7, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2 parts by mass, or any range consisting of any two of the foregoing values;
0-2 parts by mass of a processing aid; for example, 0, 0.1, 0.2, 0.3, 0.5, 0.7, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2 parts by mass, and any range of any two of the foregoing values.
In the raw material composition according to the present invention, preferably,
In the raw material composition, the raw materials are mixed,
0.6 To 15 parts by mass, preferably 1 to 9 parts by mass, of compressive property modifier; and/or the number of the groups of groups,
0.1 To 1.5 parts by mass, preferably 0.2 to 1.0 parts by mass, of a radical initiator; and/or the number of the groups of groups,
The processing aid is 0.1 to 1 part by mass, preferably 0.2 to 0.7 part by mass.
In the raw material composition according to the present invention, preferably,
The compressive property modifier is at least one of unsaturated organosilicon compounds;
Further preferably, the compressive property modifier is selected from at least one of unsaturated silanes;
Still more preferably, the compressive property modifier is at least one selected from the group consisting of triacetoxy vinylsilane, dimethoxymethyl vinylsilane, diethoxymethylvinylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyl trimethoxysilane, and tris (isopropoxy) vinylsilane.
In the raw material composition according to the present invention, preferably,
The free radical initiator is selected from at least one of peroxides; it is further preferred that the composition comprises,
The peroxide is at least one selected from acyl peroxide, alkyl hydroperoxide, dialkyl peroxide, peroxy acid, peroxy ester and peroxy ketal; it is further preferred that the composition comprises,
The acyl peroxide is selected from benzoyl peroxide, dilauroyl peroxide and 3, 5-trimethyl hexanoyl peroxide; and/or the number of the groups of groups,
The dialkyl peroxide is at least one selected from di-tert-butyl peroxide, dicumyl peroxide, cumyl peroxide butyl, 3, 5-trimethylcyclohexane-1, 1-di-tert-butyl peroxide and 2, 5-di-tert-butyl peroxide hexane; and/or the number of the groups of groups,
The alkyl hydroperoxide is at least one selected from tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, terpene hydroperoxide and tert-amyl hydroperoxide; and/or the number of the groups of groups,
The peroxyacid is at least one selected from peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, m-chloroperoxybenzoic acid, peroxydodecanoic acid and polystyrene peroxybenzoic acid; and/or the number of the groups of groups,
The peroxyester is at least one selected from tert-butyl peroxypivalate, tert-butyl peroxy2-ethylhexanoate and tert-butyl peroxybenzoate; and/or the number of the groups of groups,
The peroxyketal is at least one selected from 1, 1-bis (tertiary butyl) peroxycyclohexane, 1-di-tertiary butyl peroxy-3, 5-trimethylcyclohexane (CH 355) and 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane.
In the raw material composition according to the present invention, preferably,
The polyglycolic acid is a linear or branched polymer produced by ring-opening polymerization or polycondensation polymerization, preferably, the polyglycolic acid has a molecular weight of 20000 to 2000000g/mol; and/or the number of the groups of groups,
The processing aid is at least one selected from an antioxidant, a lubricant and a light stabilizer.
Polyglycolic acid (Polyglycolic acid, PGA) according to the present invention is also called polyglycolide or polyglycolic acid, and is the aliphatic polyester having the simplest structure. Polyglycolic acid can be prepared by ring-opening polymerization or polycondensation polymerization, specifically can be prepared by a glycolic acid melt polycondensation method and glycolic acid/ester direct condensation polymerization, and can also be prepared by glycolide ring-opening polymerization, and the melt mass flow rate is more than 1g/10 min.
Polyglycolic acid is a typical high crystallinity polymer that is lattice stable and has a relatively high melting point. However, the thermal degradation temperature is close to the melting point, degradation is easy to occur during molding and processing, and the processing temperature range is far narrower than that of other biodegradable materials, so that the service performance is influenced. PGA is extremely easy to absorb water and degrade, has poor stability, is more harsh in storage and transportation conditions, and increases cost, especially in high-temperature and high-humidity environments in summer. Polyglycolic acid has excellent biodegradability, can enter a human circulatory system to be degraded in vivo and discharged out of the body, can be degraded in an in-vitro environment, and is mainly applied to the fields of medical suture lines, drug controlled release carriers, fracture fixing materials, tissue engineering scaffolds, reinforcing materials and the like. Through solution spinning and melt spinning, polyglycolic acid can be processed into surgical suture lines, has stronger tensile strength and can maintain enough time, and is suitable for wound suturing of deep tissues.
In the raw material composition according to the present invention, preferably,
The antioxidant is at least one selected from hindered phenols and phosphite compounds; further preferably, the antioxidant is at least one selected from triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], n-stearyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, phenyl tris (2, 4-di-tert-butyl) phosphite, distearyl pentaerythritol diphosphite, and tris [2, 4-di-tert-butylphenyl ] phosphite.
In the raw material composition according to the present invention, preferably,
The lubricant is selected from stearate, ricinoleate, and amide compounds; further preferably, the lubricant is selected from the group consisting of calcium stearate, zinc ricinoleate, erucamide, ethylene bis stearamide.
In the raw material composition according to the present invention, preferably,
The light stabilizer is at least one selected from hindered amine, triazine and derivatives thereof, diphenyl ketone, salicylate, benzotriazole and derivatives thereof, cinnamic acid derivatives, zinc oxide, titanium dioxide, carbon black and tetramethylpiperidine derivatives; it is further preferred that the composition comprises,
The hindered amine is selected from N, N' -bis (2, 6-tetramethyl-4-piperidyl) -1, 6-hexamethylenediamine; and/or;
the triazine derivative is at least one selected from 2, 4-dichloro-6- (4-morpholinyl) -1,3, 5-triazine polymer and epoxy group-containing 2,4, 6-tris (2, 4-dihydroxyphenyl) -1,3, 5-triazine; and/or;
The derivative of benzotriazole is at least one selected from 2- (2 ' -hydroxy-4 ' -methoxy-phenyl) benzotriazole, 2- (2 ' -hydroxy-4 ' -ethoxy-phenyl) benzotriazole, 2- (2 ' -hydroxy-4 ' -propoxy-phenyl) benzotriazole, 2- (2 ' -hydroxy-4 ' -carboxypropoxy-phenyl) benzotriazole, 6-chloro-2- (2 ' -hydroxy-5 ' -tert-butyl-phenyl) benzotriazole, 6-chloro-2- (2 ',5' -di-tert-butyl-phenyl) benzotriazole, 2- (5 ' -methyl-phenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole; and/or the number of the groups of groups,
The cinnamic acid derivative is at least one selected from methyl methoxycinnamate, ethyl p-methoxycinnamate, isoamyl p-methoxycinnamate and isooctyl p-methoxycinnamate; and/or the number of the groups of groups,
The tetramethylpiperidine derivative is selected from 2, 6-tetramethyl-4-piperidinestearate, N-butyl-2, 6-tetramethyl-4-piperidinamine at least one of 4-amino-2, 6-tetramethylpiperidine, 1- (2-hydroxyethyl) -2, 6-tetramethyl-4-piperidinol, and polymeric derivatives thereof; still more preferably, the polymeric derivative is selected from the group consisting of styrene-4- (methacrylic acid) 2, 6-tetramethylpiperidinol ester copolymers.
It is a further object of the present invention to provide a modified polyglycolic acid having improved compression resistance comprising a polyglycolic acid backbone, grafted side chains, a coupling and/or coupling compound formed by a radical initiated intermolecular chain reaction, optionally a processing aid; the grafted side chain is at least one of a derivative, a homolog or a polymer formed by the grafting reaction of the compressive property modifier on the polyglycolic acid main chain;
Preferably from a raw material composition comprising an improved compression resistance according to one of the objects of the present invention.
In the modified polyglycolic acid having improved compression resistance according to the present invention, preferably,
The compressive strength of the modified polyglycolic acid is improved by more than 10MPa compared with that of the unmodified polyglycolic acid, and the mass flow rate of the melt is 0.1-60 g/10min;
Preferably, the compressive strength of the modified polyglycolic acid is improved by more than 15MPa compared with that of unmodified polyglycolic acid, and the mass flow rate of the melt is 5-55 g/10min;
Further preferably, the modified polyglycolic acid with improved compressive property has a compressive strength of 200MPa or more and a melt mass flow rate of 1 to 58g/10min; still further preferably, the modified polyglycolic acid having improved compression resistance has a compressive strength of 200 to 280MPa and a melt mass flow rate of 2 to 55g/10min.
Another object of the present invention is to provide a process for producing modified polyglycolic acid having improved compression resistance, comprising the steps of:
The modified polyglycolic acid is obtained by melt-reacting and extruding the raw material composition of modified polyglycolic acid having improved compression resistance according to one of the objects of the present invention.
In the production method according to the present invention, preferably,
The modified polyglycolic acid with improved compression resistance is obtained by carrying out a melting reaction on the raw material composition of the modified polyglycolic acid with improved compression resistance, plasticizing, kneading, compressing, extruding, cooling and granulating;
Preferably, the method comprises the steps of,
Preparing the modified polyglycolic acid with improved compressive property through a double-screw continuous extruder; respectively metering polyglycolic acid, a compression resistance agent, peroxide and a functional processing aid into a double-screw extruder according to a certain feeding proportion for extrusion granulation.
It is further preferred that the composition comprises,
The extrusion temperature is 180 ℃ to 260 ℃; preferably 200 ℃ to 250 ℃; such as 180, 190, 200, 210, 220, 230, 240, 250 ℃ and any range of any two values recited above; and/or the number of the groups of groups,
The rotation speed of the extruder is 50rpm to 500rpm, preferably 50rpm to 200rpm, during extrusion; and/or the number of the groups of groups,
The cooling mode is water cooling, air cooling, hot cutting air cooling, preferably air cooling.
In the production method according to the present invention, preferably,
The components including polyglycolic acid, compression resistance modifier, peroxide and functional processing aid are respectively metered into a double-screw extruder according to a certain feeding proportion for extrusion granulation. Another embodiment is to blend polyglycolic acid, compression resistance modifier, peroxide and functional processing aid in the required proportion and then add the blend to a twin screw extruder for extrusion granulation.
The instruments used in the method of the invention are all instruments conventionally used in the field.
Continuous twin-screw extrusion apparatus suitable for use in the present invention include twin-screw extruders of different designs, such as ZSK Mcc18 co-rotating parallel twin-screw extruders produced by Coperion, germany, and the like.
In the production method according to the present invention, preferably,
The preparation method of the modified polyglycolic acid with improved compressive property comprises the following steps:
and (3) carrying out melt blending extrusion on the components comprising 100 parts of polyglycolic acid, the compressive property modifier, the peroxide and the functional auxiliary agent.
Specifically, the polyglycolic acid with improved thermal stability can be obtained by adopting melt blending reaction extrusion, uniformly mixing the components with required amount in a melt state, plasticizing, kneading, compressing, extruding, cooling and granulating.
In the present invention, the radical initiator peroxide decomposes to generate radicals which abstract hydrogen from the polyglycolic acid chain, thereby allowing radicals to be present in the polyglycolic acid chain as well. These radicals may initiate the grafting reaction of the compression resistance modifiers and may also cause inter-chain reactions of polyglycolic acid molecules to form conjugates and/or conjugates.
In the above technical scheme, the inventors have surprisingly found that the graft compression resistance modification can improve the compression resistance of PGA by more than 10 MPa. Compared with the existing technologies such as micron-sized inorganic filler enhancement, the lateral group formed by the compressive property modifier with the hydrophobic property reduces the diffusion speed of water molecules in the polyglycolic acid matrix, meanwhile, the peroxide can also cause the coupling between polyglycolic acid molecular chains, and the synergistic effect of the lateral group and the peroxide inhibits the degradation of the polyglycolic acid, so that the compressive property of the lateral group is obviously improved.
The fourth object of the present invention is to provide the use of the modified polyglycolic acid having improved compression resistance as defined in the second object of the present invention or the modified polyglycolic acid produced by the production method as defined in the third object of the present invention in the fields of oil and gas exploitation, medicines, daily necessities and packaging materials.
In the application according to the invention, the method, preferably,
The modified polyglycolic acid is used as a temporary plugging ball material in the field of oil and gas exploitation; and/or the number of the groups of groups,
The modified polyglycolic acid is used as medical suture, drug controlled release carrier, fracture fixing material, tissue engineering bracket and reinforcing material in the medical field.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following advantages:
According to the invention, the compressive property of the PGA is improved by grafting and modifying the PGA through the compressive property modifier, and the toughness of the PGA is not reduced, so that a better technical effect is achieved.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The invention performs performance measurement according to the following method:
Charpy notched impact strength test: measured according to ISO 179/1eA standard using Ceast pendulum impact machine at 23℃under 50% relative humidity.
Melt Mass Flow Rate (MFR): according to ISO 1133 standard, ceast MF melt mass flow rate instrument is adopted to measure, the temperature of a charging barrel is 230 ℃, the mass load is 1.0kg, the diameter of a die is 2.095mm, the length is 8mm, the preheating time is 300s, the sample is automatically cut at intervals of set time, 5 times of average value is obtained, and the measurement result is expressed in grams per 10 minutes (g/10 min).
The method for measuring the compression resistance comprises the following steps: compression speed 5mm/min was measured according to GB/T1041-2008 using an Instron material tester at 23℃and 50% relative humidity. The spline size was 10mmx10mmx10 mm.
Molecular weight measurement: the gel permeation chromatography method is adopted to determine, PMMA is used as a standard sample, hexafluoroisopropanol is used as a mobile phase, the flow rate of the mobile phase is 1mL/min, and the column temperature is 40 ℃.
[ Example 1]
Weighing the following raw materials in proportion: 100 parts of PGA (PGS of Corbion Purac company, melt mass flow rate of 16g/10min,140 g/mol, polydispersity PDI of 1.8), 1 part of compression resistance modifier (vinyltrimethoxysilane, national medicine Co., ltd.), 0.5 part of peroxide [2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane [ national medicine Co., ltd ], 0.25 part of antioxidant 1076 (Basoff, technical grade), and 0.25 part of antioxidant 168 (Basoff). PGA, compression resistance modifier, peroxide and antioxidant were premixed and then added to a Rheomer co-rotating twin screw extruder (screw diameter 16mm, L/D=40) of Polylab system of Siemeco-flying company for extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in order, and the cooling mode was air cooling. And extruding the sample strip from a die, cooling, granulating and packaging for later use. The melt mass flow rate was determined to be 14.7g/10min. And collecting particles, and packaging for standby. The modified PGA had a molecular weight of 135000g/mol and a PDI of 1.9.
In an embodiment of the present invention, antioxidant 1076 is n-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and antioxidant 168 is tris [2, 4-di-tert-butylphenyl ] phosphite.
[ Example 2]
Weighing the following raw materials in proportion: 100 parts of PGA (Shenzhen Boli Co., melt mass flow rate of 27g/10min,130 g/mol, PDI of 2.1), 3 parts of compression resistance modifier (vinyltrimethoxysilane, produced by Guo Yao nationality), 0.5 part of peroxide [2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane [ produced by Guo Yao nationality ], 0.25 part of antioxidant 1076 (produced by Basv, technical grade), and 0.25 part of antioxidant 168 (produced by Basv). PGA, compression resistance modifier, peroxide and antioxidant were premixed and then added to a Rheomer co-rotating twin screw extruder (screw diameter 16mm, L/D=40) of Polylab system of Siemeco-flying company for extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in order, and the cooling mode was air cooling. And extruding the sample strip from a die, cooling, granulating and packaging for later use. The melt mass flow rate was determined to be 12.4g/10min. And collecting particles, and packaging for standby.
[ Example 3]
Weighing the following raw materials in proportion: 100 parts of PGA (Shenzhen Boli Co., melt mass flow rate of 27g/10min,130 g/mol, PDI of 2.1), 5 parts of compression resistance modifier (vinyltrimethoxysilane, produced by Guo Yao nationality), 0.5 part of peroxide [2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane [ produced by Guo Yao nationality ], 0.25 part of antioxidant 1076 (produced by Basf, technical grade), and 0.25 part of antioxidant 168 (produced by Basf). PGA, compression resistance modifier, peroxide and antioxidant were premixed and then added to a Rheomer co-rotating twin screw extruder (screw diameter 16mm, L/D=40) of Polylab system of Siemeco-flying company for extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in order, and the cooling mode was air cooling. And extruding the sample strip from a die, cooling, granulating and packaging for later use. The melt mass flow rate was determined to be 8.4g/10min. And collecting particles, and packaging for standby. The modified PGA has a molecular weight of 120200g/mol and a PDI of 2.0.
[ Example 4]
Weighing the following raw materials in proportion: 100 parts of PGA (PGS of Corbion Purac company, melt mass flow rate 16g/10min,140 g/mol, polydispersity PDI 1.8), 8 parts of compression resistance modifier (Tri (ethoxy) vinylsilane, manufactured by Guo Yao Chemicals Co., ltd.), 0.6 part of tert-butyl peroxybenzoate [ manufactured by Guo Yao Chen Co., ltd.), 0.3 part of antioxidant 1076 (manufactured by Basoff Co., ltd.), and 0.4 part of antioxidant 168 (manufactured by Basoff Co., ltd.). PGA, compression resistance modifier, peroxide and antioxidant were premixed and then added to a Rheomer co-rotating twin screw extruder (screw diameter 16mm, L/D=40) of Polylab system of Siemeco-flying company for extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in order, and the cooling mode was air cooling. And extruding the sample strip from a die, cooling, granulating and packaging for later use.
Comparative example 1
PGA (Shenzhen Boli Co., melt mass flow rate 27g/10min,130 g/mol, PDI 2.1) was used; the above PGA was fed into a Rheomer co-rotating twin screw extruder (screw diameter 16mm, L/D=40) from Polylab system of Siemeco-extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in order, and the cooling mode was air cooling. And extruding the sample strip from a die, cooling, granulating and packaging for later use. After extrusion, the viscosity of the sample is greatly reduced, so that the sample cannot be drawn and granulated, and the mechanical property test sample bar cannot be prepared by injection molding. The melt mass flow rate was determined to be about 200g/10min. The melt mass flow rate was determined to be about 200g/10min, the weight average molecular weight was 89000g/mol, and the PDI was 1.9.
The increase in melt mass flow rate from 27g/10min to 200g/10min after thermoplastic extrusion of PGA in comparative example 1, indicated a decrease in molecular weight after extrusion, which was thermally degraded, as evidenced by the results of molecular weight testing.
Comparative example 2
Extrusion granulation was performed using Corbion Purac PGA, brand PGS, on a Rheomer co-rotating twin screw extruder (screw diameter 16mm, L/D=40) from Polylab system of Siemens femto. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in order, and the cooling mode was air cooling. Because the viscosity of the sample is greatly reduced, the sample cannot be drawn and granulated, and the mechanical property test sample bar cannot be prepared by injection molding. The melt mass flow rate was determined to be 100g/10min.
The increase in melt mass flow rate from 16g/10min to 100g/10min after extrusion of the PGA thermoplastic of comparative example 2 indicates a decrease in molecular weight after extrusion, which occurs with thermal degradation. And the performance change amplitude is larger after the extrusion of the comparative example 1, and the mechanical performance is more reduced; the drop in amplitude of comparative example 2 is relatively small.
[ Comparative example 3]
Weighing the following raw materials in proportion: 100 parts of PGA (Shenzhen Boli Co., ltd., melt mass flow rate of 27g/10 min), 0.5 part of peroxide [2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane [ national medicine group Co., ltd. ], 0.25 part of antioxidant 1076 (Basoff, technical grade), and 0.25 part of antioxidant 168 (Basoff). PGA, compression resistance modifier, peroxide and antioxidant were premixed and then added to a Rheomer co-rotating twin screw extruder (screw diameter 16mm, L/D=40) of Polylab system of Siemeco-flying company for extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in order, and the cooling mode was air cooling. And extruding the sample strip from a die, cooling, granulating and packaging for later use. The melt mass flow rate was determined to be 23.8g/10min. And collecting particles, and packaging for standby.
[ Comparative example 4]
Weighing the following raw materials in proportion: 100 parts of PGA (Shenzhen Boli Co., ltd., melt mass flow rate of 27g/10 min), 5 parts of a compression resistance modifier (vinyltrimethoxysilane, produced by national medicine group), 0.25 part of an antioxidant 1076 (produced by Basoff, industrial grade), and 0.25 part of an antioxidant 168 (produced by Basoff). PGA, compression resistance modifier and antioxidant are premixed and then added to a Rheomer co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) of Polylab system of Siemens femto company for extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in this order. And extruding the sample strip from a die, cooling, granulating and packaging for later use. The melt mass flow rate was determined to be 120g/10min. And collecting particles, and packaging for standby.
Comparative example 5
Weighing the following raw materials in proportion: 100 parts of PGA (Shenzhen Boli Co., ltd., melt mass flow rate of 27g/10 min), 3 parts of talcum powder (D 90. Mu.m, manufactured by Suzhou Ming.) and 0.25 part of antioxidant 1076 (manufactured by Basf Co., ltd.) and 0.25 part of antioxidant 168 (manufactured by Basf Co.). PGA, talc powder and an antioxidant were premixed and then fed into a Rheomer co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) of Polylab system of Siemens femto to carry out extrusion granulation. The feeding rate was 1kg/hr. The extruder temperature was 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃ and the screw rotation speed was 100rpm in this order. And extruding the sample strip from a die, cooling, granulating and packaging for later use. The melt mass flow rate was determined to be 120g/10min. And collecting particles, and packaging for standby.
Product performance test
The products of examples 1 to 3 and comparative examples 1 to 3 were subjected to impact and compression resistance tests, and the results are shown in Table 1.
Table 1 Properties of each sample
Remarks: wherein comparative example 1 is measurement data of PGA which was not extruded through a twin screw extruder; comparative example 2 is measurement data of PGA extruded through a twin screw extruder.
As can be seen from comparison of comparative example 1 with example 2 and example 3, comparative example 1 cannot be injection molded, the compressive strength cannot be measured, and the compressive strength of the polyglycolic acid modified by the invention is obviously improved; the compression strength of the polyglycolic acid modified by the present invention is more significantly improved than the extruded PGA.
As can be seen by comparing comparative example 2 with example 1, the compressive strength of the polyglycolic acid modified in example 1 of the present invention is significantly improved.
As can be seen by comparing comparative example 3, comparative example 4 with example 3, the compression strength of the modified polyglycolic acid prepared under the combined action of the compression resistance modifier and the radical initiator is more significantly improved.
As can be seen by comparing comparative example 5 with example 2, the compressive strength of the polyglycolic acid modified by the conventional talc is not improved as much as the compressive strength of the polyglycolic acid modified by the present invention.
In conclusion, the compressive property of the PGA after the compressive property modifier and the free radical initiator are added in the invention is obviously improved compared with the unmodified PGA and the modified PGA of the inorganic filler talcum powder, and in particular, the improvement degree of the embodiment 3 is more obvious. According to the invention, the compressive property modifier and the free radical initiator are subjected to combined action through chemical reaction, and free radical coupling generated by the initiator is performed in the thermoplastic processing process, so that the hydrophobicity of the compressive property modifier slows down the diffusion of water molecules in the PGA matrix, thereby inhibiting a large number of breaks of PGA molecular chains caused by oxidization or hydrolysis, improving the compressive strength, and remarkably improving the compressive property of the PGA. At the same time, the modified polyglycolic acid of the present invention still maintains impact properties comparable to unmodified PGA.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (14)
1. A modified polyglycolic acid raw material composition with improved compression resistance, comprising the following components:
100 parts by mass of polyglycolic acid;
0.5 to 15 parts by mass of compressive property modifier;
0.01 to 2 parts by mass of a free radical initiator;
0-2 parts by mass of processing aid.
2. The modified polyglycolic acid raw material composition with improved compression resistance according to claim 1, wherein:
In the raw material composition, the raw materials are mixed,
0.6 To 15 parts by mass, preferably 1 to 9 parts by mass, of compressive property modifier; and/or the number of the groups of groups,
0.1 To 1.5 parts by mass, preferably 0.2 to 1.0 parts by mass, of a radical initiator; and/or the number of the groups of groups,
The processing aid is 0.1 to 1 part by mass, preferably 0.2 to 0.7 part by mass.
3. The modified polyglycolic acid raw material composition with improved compression resistance according to claim 1, wherein:
The compressive property modifier is at least one of unsaturated organosilicon compounds;
Preferably, the compressive property modifier is selected from at least one of unsaturated silanes;
Further preferably, the compressive property modifier is at least one selected from the group consisting of triacetoxy vinylsilane, dimethoxymethyl vinylsilane, diethoxymethylvinylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyl trimethoxysilane, and tris (isopropoxy) vinylsilane.
4. The modified polyglycolic acid raw material composition with improved compression resistance according to claim 1, wherein:
the free radical initiator is selected from at least one of peroxides; preferably, the method comprises the steps of,
The peroxide is at least one selected from acyl peroxide, alkyl hydroperoxide, dialkyl peroxide, peroxy acid, peroxy ester and peroxy ketal; it is further preferred that the composition comprises,
The acyl peroxide is selected from benzoyl peroxide, dilauroyl peroxide and 3, 5-trimethyl hexanoyl peroxide; and/or the number of the groups of groups,
The dialkyl peroxide is at least one selected from di-tert-butyl peroxide, dicumyl peroxide, cumyl peroxide butyl, 3, 5-trimethylcyclohexane-1, 1-diperoxybutyl, 2, 5-di-tert-butylperoxy hexane and 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane; and/or the number of the groups of groups,
The alkyl hydroperoxide is at least one selected from tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, terpene hydroperoxide and tert-amyl hydroperoxide; and/or the number of the groups of groups,
The peroxyacid is at least one selected from peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, m-chloroperoxybenzoic acid, peroxydodecanoic acid and polystyrene peroxybenzoic acid; and/or the number of the groups of groups,
The peroxyester is at least one selected from tert-butyl peroxypivalate, tert-butyl peroxy2-ethylhexanoate and tert-butyl peroxybenzoate; and/or the number of the groups of groups,
The peroxyketal is at least one selected from 1, 1-bis (tert-butylperoxy) cyclohexane, 1-di-tert-butylperoxy-3, 5-trimethylcyclohexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane.
5. The modified polyglycolic acid raw material composition with improved compression resistance according to claim 1, wherein:
The polyglycolic acid is a linear or branched polymer produced by ring-opening polymerization or polycondensation polymerization, preferably, the polyglycolic acid has a molecular weight of 20000 to 2000000g/mol; and/or the number of the groups of groups,
The processing aid is at least one selected from an antioxidant, a lubricant and a light stabilizer.
6. The modified polyglycolic acid raw material composition with improved compression resistance according to claim 5, wherein:
The antioxidant is at least one selected from hindered phenols and phosphite compounds; preferably, the method comprises the steps of,
The antioxidant is at least one selected from triethylene glycol bis [ beta- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate ], beta- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionate, phenyl tri (2, 4-di-tertiary butyl) phosphite, dioctadecyl pentaerythritol diphosphite and tris [2, 4-di-tertiary butylphenyl ] phosphite.
7. The modified polyglycolic acid raw material composition with improved compression resistance according to claim 5, wherein:
the lubricant is selected from stearate, ricinoleate, and amide compounds; it is further preferred that the composition comprises,
The lubricant is selected from calcium stearate, zinc ricinoleate, erucamide and ethylene bis stearamide.
8. The modified polyglycolic acid raw material composition with improved compression resistance according to claim 5, wherein:
The light stabilizer is at least one selected from hindered amine, triazine and derivatives thereof, diphenyl ketone, salicylate, benzotriazole and derivatives thereof, cinnamic acid derivatives, zinc oxide, titanium dioxide, carbon black and tetramethylpiperidine derivatives; it is further preferred that the composition comprises,
The hindered amine is selected from N, N' -bis (2, 6-tetramethyl-4-piperidyl) -1, 6-hexamethylenediamine; and/or;
The triazine derivative is at least one selected from 2, 4-dichloro-6- (4-morpholinyl) -1,3, 5-triazine polymer and 2,4, 6-tris (2, 4-dihydroxyphenyl) -1,3, 5-triazine; and/or;
The derivative of benzotriazole is at least one selected from 2- (2 ' -hydroxy-4 ' -methoxy-phenyl) benzotriazole, 2- (2 ' -hydroxy-4 ' -ethoxy-phenyl) benzotriazole, 2- (2 ' -hydroxy-4 ' -propoxy-phenyl) benzotriazole, 2- (2 ' -hydroxy-4 ' -carboxypropoxy-phenyl) benzotriazole, 6-chloro-2- (2 ' -hydroxy-5 ' -tert-butyl-phenyl) benzotriazole, 6-chloro-2- (2 ',5' -di-tert-butyl-phenyl) benzotriazole, 2- (5 ' -methyl-phenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole; and/or the number of the groups of groups,
The cinnamic acid derivative is at least one selected from methyl methoxycinnamate, ethyl p-methoxycinnamate, isoamyl p-methoxycinnamate and isooctyl p-methoxycinnamate; and/or the number of the groups of groups,
The tetramethylpiperidine derivative is selected from 2, 6-tetramethyl-4-piperidinestearate, N-butyl-2, 6-tetramethyl-4-piperidinamine at least one of 4-amino-2, 6-tetramethylpiperidine, 1- (2-hydroxyethyl) -2, 6-tetramethyl-4-piperidinol, and polymeric derivatives thereof.
9. A modified polyglycolic acid having improved compression resistance comprising a polyglycolic acid backbone, grafted side chains, a coupling and/or coupling compound formed by radical initiated intermolecular chain reaction, optionally a processing aid; the grafted side chain is at least one of a derivative, a homolog or a polymer formed by the grafting reaction of the compressive property modifier on the polyglycolic acid main chain;
preferably from a melt reaction comprising the modified polyglycolic acid feedstock composition of any one of claims 1-8 having improved compression resistance.
10. The modified polyglycolic acid having improved compression resistance according to claim 9, wherein:
The compressive strength of the modified polyglycolic acid is improved by more than 10MPa compared with that of the unmodified polyglycolic acid, and the mass flow rate of the melt is 0.1-80 g/10min;
Preferably, the compressive strength of the modified polyglycolic acid is improved by more than 15MPa compared with that of unmodified polyglycolic acid, and the mass flow rate of the melt is 0.5-60 g/10min;
Further preferably, the modified polyglycolic acid with improved compressive property has a compressive strength of 200MPa or more and a melt mass flow rate of 1 to 58g/10min; still further preferably, the modified polyglycolic acid having improved compression resistance has a compressive strength of 200 to 280MPa and a melt mass flow rate of 2 to 55g/10min.
11. The method for producing modified polyglycolic acid having improved compression resistance according to any one of claims 9 to 10, comprising the steps of:
The modified polyglycolic acid raw material composition having improved compression resistance according to any one of claims 1 to 8 is extruded after melt reaction to obtain the modified polyglycolic acid.
12. The method of manufacturing according to claim 11, wherein:
Melt blending the modified glycolic acid raw material composition with improved compression resistance according to any one of claims 1 to 8, plasticizing, kneading, compressing, extruding, cooling and granulating to obtain the modified polyglycolic acid;
Preferably, the method comprises the steps of,
Preparing the modified polyglycolic acid by a twin-screw continuous extruder;
It is further preferred that the composition comprises,
The extrusion temperature is 180 ℃ to 260 ℃; preferably 200 ℃ to 250 ℃; and/or the number of the groups of groups,
The rotation speed of the extruder is 50rpm to 500rpm, preferably 50rpm to 200rpm, during extrusion; and/or the number of the groups of groups,
The cooling mode is water cooling, air cooling, hot cutting air cooling, preferably air cooling.
13. Use of a modified polyglycolic acid according to any one of claims 9 to 10 or a modified polyglycolic acid produced by a method according to any one of claims 11 to 12 in the field of oil and gas exploitation, medicine, commodity products, packaging materials.
14. The use according to claim 13, characterized in that:
the modified polyglycolic acid with improved compressive property is used as a temporary plugging ball material in the field of oil and gas exploitation; and/or the number of the groups of groups,
The modified polyglycolic acid is used as medical suture, drug controlled release carrier, fracture fixing material, tissue engineering bracket and reinforcing material in the medical field.
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