CN116507661A - Silane modified polyester composition - Google Patents
Silane modified polyester composition Download PDFInfo
- Publication number
- CN116507661A CN116507661A CN202180078281.0A CN202180078281A CN116507661A CN 116507661 A CN116507661 A CN 116507661A CN 202180078281 A CN202180078281 A CN 202180078281A CN 116507661 A CN116507661 A CN 116507661A
- Authority
- CN
- China
- Prior art keywords
- acid
- mixture
- silane
- polyester
- polysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 235
- 229920000728 polyester Polymers 0.000 title claims abstract description 142
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 52
- -1 polysiloxane Polymers 0.000 claims abstract description 92
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000001125 extrusion Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 27
- 238000013329 compounding Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 30
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 27
- 239000004626 polylactic acid Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 150000007524 organic acids Chemical class 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 19
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000008187 granular material Substances 0.000 claims description 12
- 239000001993 wax Substances 0.000 claims description 11
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000011260 aqueous acid Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 244000068988 Glycine max Species 0.000 claims description 6
- 235000010469 Glycine max Nutrition 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 229940040102 levulinic acid Drugs 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000007799 cork Substances 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 239000000944 linseed oil Substances 0.000 claims description 4
- 235000021388 linseed oil Nutrition 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 claims description 3
- 235000006008 Brassica napus var napus Nutrition 0.000 claims description 3
- 240000000385 Brassica napus var. napus Species 0.000 claims description 3
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 claims description 3
- 235000004977 Brassica sinapistrum Nutrition 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- 244000291564 Allium cepa Species 0.000 claims description 2
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 241001474374 Blennius Species 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 241000219146 Gossypium Species 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 241000334154 Isatis tinctoria Species 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 229920001046 Nanocellulose Polymers 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 2
- 240000000111 Saccharum officinarum Species 0.000 claims description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 2
- 241000218998 Salicaceae Species 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims description 2
- 229920002522 Wood fibre Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- 239000012179 bayberry wax Substances 0.000 claims description 2
- 235000013871 bee wax Nutrition 0.000 claims description 2
- 239000012166 beeswax Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 239000004204 candelilla wax Substances 0.000 claims description 2
- 235000013868 candelilla wax Nutrition 0.000 claims description 2
- 229940073532 candelilla wax Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004203 carnauba wax Substances 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 235000003373 curcuma longa Nutrition 0.000 claims description 2
- 239000001215 curcuma longa l. root Substances 0.000 claims description 2
- 239000010696 ester oil Substances 0.000 claims description 2
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- 229920000876 geopolymer Polymers 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021374 legumes Nutrition 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
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- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
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- 238000006068 polycondensation reaction Methods 0.000 claims description 2
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- 239000004575 stone Substances 0.000 claims description 2
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- 239000003784 tall oil Substances 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
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- 238000002360 preparation method Methods 0.000 description 18
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 16
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 13
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- 239000001530 fumaric acid Substances 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a process for forming a silane-modified polyester composition. Furthermore, the invention relates to silane-modified polyester compositions obtainable by such a process and to the use of such compositions. In particular, the present invention relates to a process comprising reacting a polyester blend and a polysiloxane mixture by reactive extrusion during melt compounding to form a silane modified polyester composition.
Description
Technical Field
The present invention relates to a process for forming a silane-modified polyester composition. Furthermore, the invention relates to silane-modified polyester compositions obtainable by such a process and to the use of such compositions.
Background
Researchers have been working on developing environmentally friendly sustainable alternatives for petroleum-based non-biodegradable polymers such as Acrylonitrile Butadiene Styrene (ABS) for several years. To increase the biobased content of the material, petroleum-based polymers are typically blended with biobased polymers. In addition, studies have been made to develop complete bio-based polymers with characteristics similar to or better than petroleum-based general purpose plastics.
Polylactic acid (PLA) is a bio-based polymer with high strength and high modulus that is widely studied. PLA, however, also has some limiting properties that prevent its use in a wider range of applications, such as brittleness, poor thermal stability, low elongation at break, poor melt strength, and moisture sensitivity. Accordingly, a great deal of research has been conducted on how to improve PLA characteristics. Research includes, for example, the addition of small molecule plasticizers, blending with other ductile polymers, copolymerization, and nanocomposite materials to improve toughness and ductility of PLA and other corresponding materials. These strategies do enhance ductility and toughness, however, often at the cost of reduced strength and modulus.
In addition, inorganic reinforcing materials, inorganic powders or fibers (e.g., glass fibers), minerals, and clays have been added to polymer matrices to improve the strength and impact resistance of the polymer materials. However, such materials are difficult to uniformly disperse into the material matrix. Different surface treatment techniques can be used to improve the compatibility of the materials; however, they can make the process difficult and make mass production uneconomical.
Patent publication US20160009913A1 describes a high performance Acrylonitrile Butadiene Styrene (ABS) polymer blend comprising ABS, polylactic acid (PLA), an acrylic copolymer based lubricant and a polymer chain extender. Such blending may improve material properties; however, recycling of such materials is difficult, if not impossible.
Patent publication US20190062495A1 describes a silane modified polyester blend comprising a polyester polymer homogeneously blended with silane molecules containing two or three alkoxy groups bonded to silicon atoms. The polyester blend is prepared as follows: the solid polyester is first dissolved in an organic solvent in which both the polyester and the silane are soluble. The silane may then be dissolved into a solution containing the polyester. However, the solvents used herein (such as methylene chloride and chloroform) are harmful to human health.
Patent publication US9109083B2 describes a process for preparing a PLA resin article from a PLA composition, the process comprising blending a PLA resin under weakly acidic conditions, at least one modifier selected from the group consisting of: at least one metal/nonmetal alkoxide and at least one metal/nonmetal alkoxide having at least one functional group which is reactive with the PLA resin, or a mixture thereof. The system requires a first catalyst and, optionally, a second catalyst.
Accordingly, there is a need for biobased sustainable alternatives to traditional plastics (such as ABS), which are preferably recyclable and have good chemical resistance.
Disclosure of Invention
The present invention is directed to solving at least some of the problems of the prior art.
It is an object of the present invention to provide a chemically modified, bio-based and sustainable source material that can be used, for example, as injection molded articles for a variety of applications such as consumer products, packaging materials, automotive parts or electronic housings. The materials produced by the process of the present invention are more recyclable than the base bioplastic due to their improved chemical resistance, particularly moisture resistance and mechanical properties.
Accordingly, the present invention relates to a process for providing a novel class of preferably biobased silane modified polyester compositions. The composition is obtained by blending a polyester blend with a polysiloxane mixture and allowing them to react with each other by reactive extrusion during melt compounding.
Reactive extrusion provides a flexible alternative to polymerization in the presence of solutions or the like. Reactive extrusion is traditionally accomplished using a twin screw extruder to melt, homogenize and pump the thermoplastic polymer. Reactive extrusion occurs when a chemical reaction occurs in an extruder. The main advantage of reactive extrusion is the absence of solvent as the reaction medium. In the present invention, it has unexpectedly been found that a novel class of modified polyester compositions can be produced by reactive extrusion.
Furthermore, the use of a melt compounding process by reactive extrusion provides efficient mixing and uniform heat distribution, which enables efficient reactions between silane and polyester to occur, wherein a silane modified polyester composition is formed.
In a preferred embodiment, the polysiloxane mixture is prepared by pre-treating the silane mixture prior to reaction with the polyester blend. By mixing the polysiloxane mixture thus produced with polyester, a generally homogeneous material is obtained as a result.
Furthermore, the present invention relates to a composition obtainable by the above-described method and the use of such a composition.
In particular, the invention is characterized by what is stated in the independent claims. Some specific embodiments are defined in the dependent claims.
Several advantages are achieved using the present invention. Among other things, the method of the present invention preferably provides a bio-based and recyclable material composition. The material compositions of the present invention are generally homogeneous. The silane-modified polyester compositions of the present invention exhibit improved chemical resistance and mechanical properties, particularly strength and toughness. It also exhibits good flame retardant properties. Furthermore, the moisture resistance of the material is better than, for example, the base PLA, making it more suitable for various applications, as well as for recycling processes.
Furthermore, the present process is environmentally friendly in that it enables the formation of silane-modified polyester compositions without excessive use of solvents, since melt compounding by reactive extrusion is used, since reactive extrusion enables handling of different viscosities, wherein no dissolution of the polyester in a solvent is required. In summary, reactive extrusion provides high flexibility, enabling not only continuous processing with fast reaction times and short residence times, but also economical production of small amounts of special materials.
The material compositions of the present invention may be processed using conventional processing techniques, such as injection molding and extrusion.
Detailed Description
The present invention relates to a process for forming a modified polyester composition, in particular a bio-polyester composition, in a melt compounding process.
In the context of the present invention, the terms "bio" and "biobased" relate to polymers produced from natural sources (chemically synthesized by biological materials or completely biosynthesized by organisms).
In particular, the present invention relates to a process for forming a silane modified polyester composition, particularly a biobased silane modified polyester composition. The method includes providing a polyester blend and a polysiloxane mixture, mixing the polyester blend and the polysiloxane mixture, and finally reacting the polyester blend and the polysiloxane mixture by reactive extrusion during melt compounding.
According to one embodiment, the method includes providing one or more different polyesters, providing a polysiloxane mixture, mixing the one or more different polyesters and the polysiloxane mixture, and reacting the one or more different polyesters and the polysiloxane mixture during melt compounding by reactive extrusion.
According to one embodiment, the polyester blend and polysiloxane mixture may be mixed in separate containers prior to being fed into the extruder, wherein the components are fed together into the extruder.
According to another embodiment, the polyester blend and the polysiloxane mixture may be mixed in an extruder, i.e., the components may be fed separately into the extruder.
According to a preferred embodiment, the polyester blend is provided in solid form, preferably as pellets. The pellets are typically dried before mixing with the polysiloxane mixture or before feeding into the extruder because the polyester typically absorbs some moisture from the air, which can lead to decomposition of the material during high temperature processing.
The polyester blend comprises one or several different polyesters. For example, two different polyesters may be combined. According to one embodiment, the polyester blend comprises a polyester selected from the group of: polylactic acid, polylactide, polybutylene succinate, polyhydroxyalkanoate, polyhydroxybutyrate, cork fat, and combinations thereof.
According to a preferred embodiment, the polyester is polylactic acid. Preferably at least 80wt.%, more preferably at least 90wt.% of the polyester is polylactic acid.
According to one embodiment, a portion of the polyesters in the polyester blend may be replaced by: polyethylene (PE), preferably bio-based PE; or polyethylene terephthalate (PET), preferably bio-based PET; or polypropylene (PP), preferably bio-based PP; or Thermoplastic Polyurethane (TPU), preferably a bio-based TPU; or Polyamide (PA), preferably biobased PA; or cellulose esters such as Cellulose Acetate (CA), cellulose Acetate Butyrate (CAB) and Cellulose Acetate Propionate (CAP); or a mixture thereof. Preferably, the amount of PE, PET, PP, TPU, PA, cellulose ester, or mixture thereof in the polyester blend is at most 49wt.%, for example 5 to 35wt.%, more preferably 10 to 20wt.%, based on the total weight of the polyester blend. PE, PET, PP, TPU, PA and/or cellulose esters can be used to enhance the elastic and mechanical properties of the composition.
According to one embodiment, if the polyester blend comprises more than one type of polyester, the polyester blend may be formed by melt compounding the polyesters into one compound or at least a complex. In this case, the polyester is preferably dried overnight before melt compounding and then extruded using an extrusion temperature of about 200℃and a screw speed of about 55 to 65rpm or preferably about 55 to 350 rpm. According to one embodiment, a stereocomplex polyester is obtained.
According to another embodiment, the different polyesters are mixed with each other either before being fed into the extruder or manually in the extruder.
The same applies to the optional polyethylenes, polyethylene terephthalates, polypropylenes, thermoplastic polyurethanes, polyamides and cellulose esters, i.e. they may be melt compounded with the polyester in a separate melt compounding step to one compound or at least a compound, or they may be mixed with the polyester manually before being fed into the extruder or in the extruder.
Thus, according to one embodiment, one or several separate polyester blends may be used and then mixed in an extruder.
The melting temperature of the polyester used in the present invention is generally in the range of 40 to 300 ℃, preferably in the range of 80 to 200 ℃, and most preferably in the range of 100 to 180 ℃.
Preferably, the melt flow index of the polyester blend is in the range of 1g/10min to 50g/10min, preferably in the range of 5g/10min to 25g/10min, e.g. the melt flow index is 10g/10min. The melt flow index is measured by a measurement method comprising charging plastic polyester particles into a capillary tube having a temperature of 190 ℃. A piston and a weight of 2.16kg were placed on top of the pellet. Under the action of the weight, the molten polyester is extruded from the capillary over a period of time to give a melt flow index.
According to a preferred embodiment, the polysiloxane mixture is provided in liquid form. In the present invention, the term "liquid form" also includes solutions. Thus, according to the invention, a material is in a liquid state if it is itself liquid, or dissolved or at least dispersed in a medium, preferably in a solvent.
According to one embodiment, the polysiloxane mixture consists of silane monomers, oligomers or polymers, or any mixture of these. Furthermore, the polysiloxane mixture may comprise modified or unmodified silanes.
According to a preferred embodiment, the polysiloxane mixture is prepared by pre-treating a silane mixture. Pretreatment greatly improves the reactivity of the silane, wherein the polysiloxane mixture formed reacts more efficiently with the polymer matrix during melt compounding. According to one embodiment, the polysiloxane mixture is formed by mixing one or several different silane monomers, preferably at room temperature.
According to one embodiment, the polysiloxane mixture is composed of silane monomers having at least one functional group. Preferably, the monomer is selected from the group of: methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), 3-glycidoxypropyl-trimethoxysilane (GPTMS), bis (triethoxysilyl) ethane (BTESE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS), and (3-aminopropyl) triethoxysilane (APTES), and combinations thereof.
According to another embodiment, the polysiloxane mixture consists of silane monomers selected from the group of: triethoxysilane, trimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, methyldiethoxyvinylsilane, 1, 2-bis (trimethoxysilyl) ethane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, phenyltrimethoxysilane, n-butyltriethoxysilane, n-octadecyltriethoxysilane, acryloxypropyl-trimethoxysilane, allyltrimethoxysilane, aminopropyl trimethoxysilane, methacryloxypropyl triethoxysilane, methacryloxypropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, diphenylsilanediol, 1, 2-bis (trimethoxysilyl) methane, 1, 2-bis (trimethoxysilyl) ethane, epoxycyclohexylethyltrimethoxysilane, 1- (2- (trimethoxysilyl) ethyl) cyclohexane-3, 4-epoxide, glycidyl methacrylate, and mixtures thereof. These may be used alone, in combination with each other, or together with the above-mentioned silane monomers.
According to one embodiment, at least part of the silane monomers are monomers having functional groups. Preferably at least 50mol-%, preferably at least 70mol-%, more preferably at least 90mol-% of the monomers have functional groups.
According to one embodiment, at least 50mol-%, preferably at least 70mol-%, more preferably at least 90mol-% of the silane monomers are selected from the group of: difunctional and trifunctional silanes including Methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), and combinations thereof. These monomers are especially reactive and compatible with the polyester matrix and they also provide improved chemical resistance.
According to one embodiment, all silane monomers are selected from the group of: difunctional and trifunctional silanes including Methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), and combinations thereof.
Thus, according to one embodiment of the present invention, the polysiloxane mixture is prepared by pre-treating a silane mixture comprising any of the above-described silane monomers.
According to a preferred embodiment, the silane mixture is pretreated, i.e. a polysiloxane mixture is formed, prior to mixing with the polyester blend.
Preferably, the silane monomers of the silane mixture are hydrolyzed during the pretreatment. In hydrolysis, possible ethoxy and methoxy groups of, for example, silanes are reacted with hydroxyl groups (OH), i.e. silanol, which can further react with other siloxanes or silanol in the mixture and form, for example, dimers and trimers, and these hydroxyl groups also subsequently react with the polymer matrix. Thus, according to one embodiment, the polysiloxane mixture may consist of silanes, siloxane dimers or oligomers, or any mixture of these.
Thus, according to one embodiment, the polysiloxane mixtures are prepared in the liquid state by hydrolysis and polycondensation of the corresponding monomers, in order to obtain polymers having a siloxane skeleton formed by repeating-Si-O-Si-units. The properties of the siloxane formed, such as molecular weight, can be controlled by hydrolysis and condensation conditions. By changing the conditions, different structures are formed, such as linear structures, branched structures and more branched structures. The degree of condensation of the siloxanes can also be adjusted to a suitable level.
According to one embodiment, pH and temperature conditions may be used to influence the properties of the polysiloxane mixture formed. In general, alkaline conditions favor condensation rather than hydrolysis. By varying the pH conditions and temperature, the polysiloxane compound structure and its reactivity can be "manipulated". For example, more OH-groups may be introduced into the structure to increase the reactivity of the compound.
According to one embodiment, the polysiloxane mixture may comprise a partially or fully condensed polysiloxane polymer having at least one functional group reactive with the polyester.
Hydrolysis and condensation of the corresponding monomers can be carried out under acidic, basic or neutral conditions.
According to one embodiment, the silane is hydrolyzed with an aqueous acid solution, wherein the acid is preferably an organic acid. The acid content of the aqueous acid solution is generally in the range of 0.5 to 5mol-%, for example 1mol-%, of the aqueous acid solution.
One or more organic acids may be used simultaneously.
The acid acts as a catalyst during the hydrolysis reaction. In addition, the acid improves the compatibility of the polysiloxane with the polymer matrix, i.e., the polyester, because the acid can also react with the polyester.
According to another preferred embodiment, the organic acid comprises monomeric organic acids, wherein the polyester is coupled with the polysiloxane at least in part using these monomeric organic acids in melt compounding. Thus, the organic acid can be bound to the polymer backbone, wherein no deleterious acid remains free.
According to yet another preferred embodiment, the organic acid used is multifunctional, in particular difunctional, wherein the organic acid can react from both ends with the polysiloxane and/or the polyester. Preferably, the organic acid has groups that are reactive with at least the end groups of the polyester.
According to one embodiment, the organic acid monomer reacts with the monomer corresponding to the polysiloxane polymer and thereby becomes part of the polysiloxane formed.
According to one embodiment, the polysiloxane mixture is formed in the presence of an acid selected from the group of: inorganic acids including nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid; or a group of: organic acids including lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, itaconic acid, fumaric acid, succinic acid, biosuccinic acid, gluconic acid, glutamic acid, malic acid, maleic acid, 2, 5-furandicarboxylic acid, 3-hydroxypropionic acid, glucaric acid, aspartic acid, levulinic acid, and combinations thereof.
According to a preferred embodiment, the acid is a multifunctional organic acid, such as levulinic acid, succinic acid, malic acid, maleic acid, adipic acid, sebacic acid, or any combination thereof. Preferably, the acid is succinic acid, more preferably bio-succinic acid. Biosuccinic acid is a renewable alternative to traditional biosuccinic acid, which is generally produced from sustainable biomass by fermentation processes. Biosuccinic acid has been found to be particularly compatible with polyesters. According to one embodiment, the biosuccinic acid solution is formed by diluting 1mol-% biosuccinic acid in deionized water.
Also, one or more organic acids may be used simultaneously. According to one embodiment, the at least one organic acid is difunctional, such as oxalic acid, malonic acid, succinic acid, DL-malic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, L- (+) -tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid. According to another embodiment, at least two, e.g., 2 or 4, organic acids are difunctional. According to another embodiment, one or more difunctional acids are used in combination with one or more monofunctional acids.
According to one embodiment, at least 50mol-%, preferably at least 60mol-%, more preferably at least 80mol-% of the organic acids are difunctional.
Thus, according to a preferred embodiment, the silane is hydrolyzed with an aqueous solution of an organic acid, wherein the organic acid is at least mainly a difunctional organic acid such as succinic acid, optionally in combination with other organic acids as auxiliary acids such as monofunctional organic acids.
Thus, according to one embodiment, the polysiloxane mixture is prepared by pre-treating a silane mixture by mixing the silane and an aqueous acid solution, preferably at room temperature. Preferably, the polysiloxane mixture is prepared by gradually adding an aqueous acid solution, such as bio-succinic acid aqueous solution, to a reaction vessel containing silane. The mixture is preferably mixed for more than one hour, preferably more than 6 hours, for example 12 hours.
According to another embodiment, the polysiloxane mixture is prepared by mixing silane and DI water by stirring at room temperature. The stirring time may be different; typically the stirring time is more than one hour, preferably more than 6 hours, for example 12 hours.
According to one embodiment, the weight ratio of aqueous acid to silane is in the range of 1:20 to 2:3, preferably in the range of 1:10 to 1:3, for example 3:10.
According to one embodiment, the polysiloxane mixture may comprise one or several different types of siloxanes. More than one individual polysiloxane mixture may also be used. Thus, more than one type of polysiloxane may be mixed with each other prior to mixing with the polyester blend. According to another embodiment, two or more polysiloxane mixtures may be formed and then added separately to the polyester blend.
According to a preferred embodiment, the polysiloxane mixture in liquid form is mixed with the polyester blend in solid form (preferably as pellets), i.e. the polysiloxane mixture and the polyester blend are mixed prior to melt compounding, wherein the liquid polysiloxane mixture stays on the surface of the polyester and once the polyester melts, the reaction takes place during extrusion.
According to another embodiment, the polysiloxane mixture in liquid form is mixed with the molten polyester using a liquid feed, wherein the reaction occurs during extrusion once the components are mixed with each other.
Thus, according to one embodiment of the present invention, the present process for forming a silane modified polyester composition, in particular a biobased silane modified polyester composition, comprises the steps of:
-providing a blend of polyesters which is a blend of,
-providing a mixture of polysiloxanes,
-mixing said polyester blend and said polysiloxane mixture, and
-reacting the polyester blend and the polysiloxane mixture by reactive extrusion during melt compounding.
The material composition of the present invention is based on interactions between inorganic and organic substances. In this material, the polysiloxane and polyester react during reactive extrusion by forming chemical bonds, such as covalent bonds, with each other. According to one embodiment, the acid optionally used as catalyst may also form chemical bonds with the polysiloxane and/or polyester.
According to a preferred embodiment, the material composition of the invention is homogeneous. In the present invention, the term "homogeneous" means a material that is homogeneous throughout the composition, and that cannot be mechanically separated into different materials.
According to one embodiment, the polysiloxane content is 0.1 to 20wt.%, preferably 0.1 to 10wt.%, by weight of the total polyester composition.
According to one embodiment, the weight ratio between polyester and polysiloxane in the material composition is 1:99 to 99:1, e.g. 10:99 or 99:10 or 20:80 or 80:20 or 30:70 or 70:30 or 50:50.
According to a preferred embodiment, the weight ratio between polyester and polysiloxane in the material composition is in the range of 80:20 to 99.9:0.1, for example 99.5:0.5.
According to one embodiment, the composition of the invention further comprises fillers, in particular inorganic fillers, such as ash, minerals, mineral sludge, clay, ceramics and other inorganic substances including, for example, calcium carbonate, kaolin, talc, gypsum, chalk, mica, wollastonite, glass, silica, alumina, titania and other inorganic oxides; crushed masonry, concrete and other stone and sand-like materials; diatomaceous earth; metal hydrates such as aluminum hydroxide (aluminum hydrate), calcium hydroxide (calcium hydrate); geopolymers, and the like.
According to one embodiment, the composition of the invention further comprises additives, in particular plasticizers, such as glycerol, polyethylene glycol, triethyl citrate, tributyl citrate, acetyl tributyl citrate; vegetable oils such as soybean oil, linseed oil, tall oil, castor oil, canola (canola); or modifications thereof such as maleated, acrylated, ethylenated, succinated, epoxidized, hydroxylated vegetable oils or other vegetable ester oils or resins, including epoxidized soybean oil, maleated soybean oil, epoxidized linseed oil; or any combination thereof.
According to one embodiment, the composition of the invention further comprises additives, in particular lubricants, including stearates, such as calcium stearate and magnesium stearate; and natural waxes such as palm wax, soybean wax, beeswax, sugarcane wax, tapioca wax, candelilla wax, rice bran wax, berry wax (berry wax), bayberry wax, and month Gui La; or any mixture thereof.
According to one embodiment, the composition comprises organic fillers and colorants, such as wood, and plant-based materials and parts and side streams thereof, including legumes, such as soybean, soybean hulls, wheat hulls, and rice hulls; seaweed; algae; natural resins and gums; carbon; carbon black; biochar; isatis tinctoria; willows and other bark; onion skins and other vegetable skins; lemon; turmeric root; all natural fibers such as cotton, hemp, flax, pulp, wood fibers; and components thereof, such as lignocellulose, lignin, cork fat; polysaccharides, including natural polysaccharides such as cellulose, starch and hemicellulose, nanocellulose and derivatives thereof; and any combination thereof.
According to one embodiment, the composition of the invention further comprises a chain extender and/or a crosslinking agent, such as a peroxide, epoxide, amine or acrylic functional chain extender. In a preferred embodiment, the amount of chain extender/cross-linker, especially peroxide, is less than 0.5wt.%, preferably from 0.01 to 0.2wt.%, calculated on the total weight of the composition. Chain extenders/crosslinkers can be used to increase the viscosity of the composition. In some applications, such as, for example, in film applications, higher viscosity, i.e., less flowable, compositions may be preferred. In addition, the chain extender/crosslinker increases the durability of the composition by forming bonds between the polymer chains. According to a preferred embodiment, such components are added to the composition of the invention after formation of the silane-modified polyester in a separate process step. According to another embodiment, such components may be added to the composition at the end of the reactive extrusion process, wherein the silicone and polyester have substantially reacted.
The polyester blend and polysiloxane mixture are reacted into a composition during the melt compounding process by reactive extrusion. The components do not react until the polyester is at least substantially melted during the extrusion stage.
Extrusion in a melt compounding process according to the present invention includes feeding the components into an extruder, heating the components, or at least the polyester, to initiate a chemical reaction. As mentioned above, the polysiloxane mixture may be mixed with the polyester blend prior to feeding into the extruder, or they may be mixed in the extruder once the polyester blend is melted by the liquid supply of the polysiloxane mixture.
Typically, the extruder reactor used in the present invention is a twin screw extruder, preferably a co-rotating twin screw extruder. Twin screw extruders have excellent mixing capabilities at the molecular level, which enables the production of homogeneous material compositions.
Preferably, the reactive extrusion is performed at a temperature above the melting temperature of the polyester blend. According to a preferred embodiment, the reactive extrusion is carried out at a temperature of at least 190 ℃, for example at about 200 ℃.
The screw speed for extrusion is preferably in the range of 50 to 350rpm or 50 to 200rpm, more preferably in the range of 50 to 200rpm or 50 to 100rpm, for example 150rpm or 65rpm.
During extrusion, the components are compounded into a silane-modified polyester composition.
According to one embodiment, the mixture is compounded into strands in extrusion. In another embodiment, the strands are optionally cooled in a water bath. Finally, the cooled strands may be granulated into granules.
According to one embodiment, the process of the present invention may be repeated for the silane-modified polyester composition formed in the present invention in order to further modify the properties of the composition. For example, according to one embodiment of the present invention, the silane modified polyester composition may be combined with another polyester blend.
According to one embodiment, the process of the present invention may comprise foaming the obtained polyester composition to obtain a foamed silane-modified polyester composition. The composition may be foamed by any known foaming method, such as by chemical or physical foaming, using, for example, foam extrusion and carbon dioxide, nitrogen, pentane, or any combination thereof as a blowing agent.
The invention also relates to a preferably bio-based silane modified polyester composition obtainable by the process of the invention.
Furthermore, the present invention relates to the use of the preferably bio-based silane modified polyester composition obtained by the process of the present invention. The materials are suitable for injection molding and extrusion, in particular they are suitable as packaging materials, for example for cosmetic packaging.
It is to be understood that the disclosed embodiments of the invention are not limited to the specific structures, process steps, or materials disclosed herein, but are extended to equivalents thereof as would be recognized by those of ordinary skill in the relevant arts. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Reference throughout this specification to one embodiment or embodiment means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. When a term is used, such as, for example, about or substantially where the value is referred to, it is also disclosed.
As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be understood as though each member of the list is individually identified as a separate and unique member. Thus, any individual member of such list should not be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary. In addition, various embodiments and examples of the invention, as well as alternatives to the various components thereof, may be mentioned herein. It should be understood that these embodiments, examples and alternatives are not to be construed as actual equivalents of each other, but rather as separate and autonomous representations of the invention.
Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In this description, numerous specific details are provided, such as examples of lengths, widths, shapes, etc., to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, etc.
While the foregoing examples illustrate the principles of the invention in one or more specific applications, it will be apparent to those of ordinary skill in the art that numerous modifications in form, usage and implementation details can be made without the exercise of inventive faculty, without departing from the principles and concepts of the invention. Accordingly, the invention is not intended to be limited except as by the following claims.
The following non-limiting examples are only intended to illustrate the advantages obtained with embodiments of the present invention.
Examples
Example 1
Preparation of mixture 1 (polysiloxane mixture)
57.5g of an aqueous solution of biosuccinic acid (1 wt.% biosuccinic acid diluted in deionized water) was gradually added to 425g of methyltriethoxysilane, 32.5g of ethoxytrimethylsilane and 15.5g of bis (triethoxysilyl) ethane. The solution was mixed at room temperature for 6 hours before use.
Preparation of composition 1 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L130) having a Melt Flow Index (MFI) of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃ and then mixed with mixture 1 in a weight ratio of 99.5:0.5 prior to melt compounding. The obtained mixture was melt compounded using twin-screw extrusion at an extrusion temperature of 200℃and a screw rotation speed of 65 rpm. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 2
Preparation of composition 2 (silane-modified polyester)
Composition 1 of example 1 was mixed with commercial grade polybutylene succinate (BioPBS FZ 71) having an MFI of 22g/10min (190 ℃,2.16 kg) in a weight ratio of 90:10. The prepared mixture was melt compounded by using twin screw extrusion. Extrusion was carried out at a temperature of 200℃and a screw speed of 65 rpm. The mixture was extruded into strands, cooled in a water bath and granulated into granules.
Example 3
Preparation of polyester blends
A95:5 w/w mixture of commercial grade polylactic acid (Luminuy L130) having an MFI of 10g/10min (190 ℃,2.16 kg) and poly D-lactic acid (Luminuy D120) having an MFI of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃ and then melt compounded into a solid composite polylactic acid using an extrusion temperature of 200 ℃ and a screw speed of 65 rpm. The obtained mixture was granulated and dried overnight in a circulating air oven at 60 ℃.
Preparation of composition 3 (silane-modified polyester)
The polyester blend thus obtained was mixed with mixture 1 of example 1 in a weight ratio of 99.5:0.5. Then, it was melt compounded at a screw speed of 65rpm at a temperature of 200℃using twin screw extrusion. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 4
Preparation of mixture 2 (polysiloxane mixture)
2.3g of an aqueous solution of biosuccinic acid (1 wt. -% of biosuccinic acid diluted in deionized water) was gradually added to 10g of dimethyldiethoxysilane. The resulting solution was mixed at room temperature for 12 hours before use.
Preparation of composition 4 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L130) having a melt flow index of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃ and then mixed with mixture 2 at a weight ratio of 98:2. The obtained mixture was melt compounded by using twin-screw extrusion at a screw speed of 65rpm at an extrusion temperature of 200 ℃. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 5
Preparation of mixture 3 (polysiloxane mixture)
6.66g of Methyltriethoxysilane (MTEOS) and 5.54g of dimethyldiethoxysilane (DMDEOS) were combined in a dryer. 2.68g of an aqueous solution of bio-succinic acid (1 wt. -% of bio-succinic acid was diluted in deionized water) was gradually added to the mixture. The mixture was mixed at room temperature for 12 hours before use.
Preparation of composition 5 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L130) having a melt flow index of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃ and then mixed with mixture 3 at a weight ratio of 98:2. The obtained mixture was melt compounded at a screw speed of 65rpm using twin screw extrusion at a temperature of 200 ℃. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 6
Preparation of mixture 4 (polysiloxane mixture)
2.87g of an aqueous solution of biosuccinic acid (2 wt. -% of biosuccinic acid diluted in deionized water) was gradually added to 10g of methyltriethoxysilane and 1.3g of phenyltrimethoxysilane. The solution was mixed at 40 ℃ for 4 hours before use.
Preparation of composition 6 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L130) having a melt flow index of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃. Then, 1wt.% of mixture 4 and 1wt.% of mixture 2 of example 4 were added to PLA before melt compounding. The compound was then melt compounded by using twin screw extrusion at a screw speed of 65rpm at a temperature of 200 ℃. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 7
Preparation of composition 7 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L130) having a melt flow index of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃. PLA pellets were mixed with epoxidized soybean oil (ESBO) and with mixture 1 of example 1 in a weight ratio of 94.5:5:0.5. The mixture was compounded using twin screw extrusion at a screw speed of 65rpm at a temperature of 200 ℃. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 8
Film samples were prepared with a thickness of about 0.2mm by compression molding (190 ℃ C., 100kN force) of the silane-modified polyesters of the previous examples, acrylonitrile Butadiene Styrene (ABS) and poly (l-lactic acid) (PLLA) reference materials. Samples were cut from the films and their tensile properties were measured according to ISO 527-3, which describes a test method for determining the tensile properties of plastic films and sheets. Test speeds were measured using sample types 5 and 5 mm/min. The results are shown in table 1.
Table 1. The mechanical properties of the prepared silane modified polyester compositions and the properties of ABS and PLLA reference materials.
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The results in table 1 show that the tensile strength of the silane modified polyesters is 23% to 53% higher than the ABS reference and, in the case of example 4 and example 6, the strength is similar to the PLLA reference. The modulus of elasticity of the samples was 40% to 58% higher than that of the ABS reference and 3% to 16% higher than that of the PLLA reference. For examples 2 and 7, the toughness of the samples was improved because the elongation at break values were 228% (27.6%) and 791% (74.9%) higher than the elongation at break values of the ABS reference.
Example 9
The properties of the silane-modified polyesters according to the previous examples were studied and compared with the reference materials ABS and PLLA. The results of each experiment are presented in figures 1 to 4.
In the first experiment, the change in sample weight after exposure to water vapor at 100 ℃ for 4 hours was studied. Disc-shaped samples (approximately 5g each) were exposed to water vapor for 4h, dried at 60 ℃ for 12h, and weighed. The change in sample weight is calculated as the change in mass divided by the initial mass and multiplied by 100. The results are shown in FIG. 1, and it can be seen from FIG. 1 that the silane-modified polyesters (examples 1-7) have a much lower moisture absorption (0% to 0.3%) than the reference PLLA (3.7%), and in the case of examples 1-4 and 6-7, even lower moisture absorption than ABS (0.3%).
In a second experiment, the change in sample weight after exposure to 1m NaOH 72h at room temperature was studied. Disc-shaped samples (approximately 5g each) were immersed in NaOH solution for 72h, dried at 60 ℃ for 12h, and weighed. The change in sample weight is calculated as the change in mass divided by the initial mass and multiplied by 100. The results are shown in fig. 2. For the ABS reference, a 1% weight change was observed, whereas for the silane-modified polyesters of the invention, the weight change was lower, ranging from 0.04 to 0.78%. The weight change of example 1 was the lowest (0.04%) and was similar to the weight change of the PLLA reference sample (0.06%).
In a third experiment, the change in sample weight after 168h exposure to a perfume mimetic solution consisting of 80wt.% ethanol, 10wt. -% turpentine and 10wt. -% phthalate was investigated at room temperature. Disc-shaped samples (approximately 5g each) were immersed in the perfume mimic for 168h, dried at 60 ℃ for 12h, and weighed. The change in sample weight is calculated as the change in mass divided by the initial mass and multiplied by 100. The results are shown in fig. 3. The weight change of PLLA and ABS references after exposure to perfume mimetic solutions was 1.0% and 0.5%, respectively. For silane modified polyesters, the weight change is lower than or at the same level as the ABS reference, i.e., between 0.04% and 0.5%. Examples 1 and 2 were the most durable against exposure to perfume mimics, with weight changes of 0.04% and 0.3%, respectively.
In a fourth experiment, the absorption of essential oils (100% lavender oil, 72h at room temperature) was investigated. 3 to 5 drops of essential oil were carefully placed on top of the disk-shaped sample. After 72h, the sample was thoroughly wiped with a paper towel to remove oil and then weighed. The oil absorption is calculated as the change in mass of the sample divided by the initial mass of the added essential oil and multiplied by 100. The results are shown in fig. 4. The oil absorption was 25% and 26% for ABS and PLLA references, respectively. For the silane-modified polyesters in examples 1 and 3, the oil absorption was lower, 7% (example 1) and 16% (example 3). On the other hand, the oily component in example 7 resulted in a higher oil absorption of the sample, 37%.
Example 10
Preparation of mixture 5 (polysiloxane mixture)
42.5g of an aqueous levulinic acid solution (1 wt. -% levulinic acid diluted in deionized water) is gradually added to a mixture of 350g methyltriethoxysilane, 127.5g dimethyldiethoxysilane and 12.5g methoxytrimethylsilane. The solution was mixed at room temperature for 12 hours before use.
Preparation of composition 8 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L130) having a melt flow index of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃. PLA pellets were mixed with mixture 5 in a weight ratio of 98:2. The mixture was compounded using twin screw extrusion at a screw speed of 65rpm at a temperature of 200 ℃. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 11
Preparation of mixture 6 (polysiloxane mixture)
75g of an aqueous maleic acid solution (0.5 wt. -% maleic acid diluted in deionized water) are gradually added to a mixture of 375g of dimethyldiethoxysilane and 32.5g of 3-glycidoxypropyl trimethoxysilane. The solution was mixed at room temperature for 2.5 hours. After mixing, the alcohol formed is evaporated with a rotary evaporator before use.
Preparation of composition 9 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L175) having a melt flow index of 3g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃. PLA pellets were used in a weight ratio of 98:2 to mixture 6. The mixture was compounded using twin screw extrusion at a screw speed of 100rpm at a temperature of 200 ℃. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Example 12
Preparation of mixture 7 (polysiloxane mixture)
67g of an aqueous solution of biosuccinic acid (1.3 wt-% biosuccinic acid diluted in deionized water) were gradually added to 575g of methyltriethoxysilane. The solution was mixed at room temperature for 12 hours before use.
Preparation of composition 10 (silane-modified polyester)
Commercial grade polylactic acid (Luminuy L130) having a Melt Flow Index (MFI) of 10g/10min (190 ℃,2.16 kg) was dried overnight in a circulating air oven at 60 ℃ and then mixed with mixture 7 in a weight ratio of 98:2 prior to melt compounding. The obtained mixture was melt compounded using twin-screw extrusion at an extrusion temperature of 200℃and a screw rotation speed of 70 rpm. The composite material was extruded into strands, cooled in a water bath and granulated into granules.
Industrial applicability
The present process is useful for producing silane-modified polyester compositions, particularly biobased silane-modified polyester compositions, generally in lieu of conventional processes for producing silane-modified polymers.
In particular, the present material compositions are useful alternatives to ABS in fossil-based thermoplastics such as objects manufactured by injection molding or melt extrusion. The composition may be used, for example, as a consumer product for cosmetic or food packaging materials (covers, lids, etc.).
List of references
Patent literature
US20160009913A1
US20190062495A1
US9109083B2
Claims (20)
1. A method for forming a biobased silane modified polyester composition comprising the steps of:
-providing a blend of polyesters which is a blend of,
-providing a mixture of polysiloxanes,
-mixing said polyester blend and said polysiloxane mixture, and
-reacting the polyester blend and the polysiloxane mixture by reactive extrusion during melt compounding.
2. The method of claim 1, wherein the polyester blend comprises one or several different polyesters.
3. The process according to claim 1 or 2, wherein the polyester blend is provided in solid form, preferably as pellets.
4. The method of any of the preceding claims, wherein the polyester blend comprises a polyester selected from the group of: polylactic acid, polylactide, polybutylene succinate, polyhydroxyalkanoate, polyhydroxybutyrate, cork fat, and combinations thereof.
5. The method according to any of the preceding claims, wherein a portion of the polyester in the polyester blend, preferably up to 49wt.%, such as 5 to 35wt.%, more preferably 10 to 20wt.% of the total weight of the polyester blend, is replaced by Polyethylene (PE), or polyethylene terephthalate (PET), or polypropylene (PP), or Thermoplastic Polyurethane (TPU), or Polyamide (PA), or cellulose ester, or mixtures thereof.
6. A method according to any one of the preceding claims, wherein the polysiloxane mixture is prepared by pre-treating a silane mixture by means of hydrolysis and polycondensation of the corresponding monomers.
7. The method according to claim 6, wherein the silane mixture is hydrolyzed with an aqueous acid solution, wherein the acid is preferably an organic acid, in particular a multifunctional organic acid, such as levulinic acid, succinic acid, malic acid, maleic acid, adipic acid or a combination thereof, in particular biosuccinic acid.
8. The method according to claim 7, wherein the acid is an organic acid and at least 50mol-%, preferably at least 60mol-%, more preferably at least 80mol-% of the organic acid is difunctional.
9. The method of any of the preceding claims, wherein the polysiloxane mixture consists of silane monomers, oligomers or polymers, or any mixture thereof, and wherein the silane may be modified or unmodified.
10. A method according to any one of the preceding claims, wherein the polysiloxane is composed of silane monomers having at least one functional group, preferably the monomers are selected from the group of: methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), 3-glycidoxypropyl-trimethoxysilane (GPTMS), bis (triethoxysilyl) ethane (BTESE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS), and (3-aminopropyl) triethoxysilane (APTES), and combinations thereof, more preferably, the monomers are selected from the group of: methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), and combinations thereof.
11. The method according to any of the preceding claims, wherein the polysiloxane is composed of silane monomers, wherein at least 50mol-%, preferably at least 70mol-%, more preferably at least 90mol-% of the silane monomers are selected from the group of: difunctional and trifunctional silanes including Methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), and combinations thereof.
12. The method of any of the preceding claims, wherein the polysiloxane content is 0.1 to 10wt.% of the weight of the entire polyester composition.
13. The method of any preceding claim, wherein the composition further comprises:
fillers, in particular inorganic fillers, such as ash, minerals, mineral sludge, clays, ceramics and other inorganics, including for example calcium carbonate, kaolin, talc, gypsum, chalk, mica, wollastonite, glass, silica, alumina, titania and other inorganic oxides; crushed masonry, concrete and other stone and sand-like materials; diatomaceous earth; metal hydrates such as aluminum hydroxide, calcium hydroxide; geopolymers, and the like; or any combination thereof, and/or
Additives, in particular plasticizers, such as glycerol, polyethylene glycol, triethyl citrate, tributyl citrate, acetyl tributyl citrate; vegetable oils such as soybean oil, linseed oil, tall oil, castor oil, canola; or modifications thereof such as maleated, acrylated, ethylenated, succinated, epoxidized, hydroxylated vegetable oils or other vegetable ester oils or resins, including epoxidized soybean oil, maleated soybean oil, epoxidized linseed oil; or any combination thereof.
14. The method of any of the preceding claims, wherein the composition further comprises:
Organic fillers and colorants, such as wood or plant-based materials or parts and side streams thereof, including legumes, such as soybean, soybean hulls, wheat hulls, and rice hulls; seaweed; algae; natural resins and gums; carbon; carbon black; biochar; isatis tinctoria; willows and other bark; onion skins and other vegetable skins; lemon; turmeric root; all natural fibers such as cotton, hemp, flax, pulp, wood fibers; and components thereof, such as lignocellulose, lignin, cork fat; polysaccharides, including natural polysaccharides such as cellulose, starch and hemicellulose, nanocellulose and derivatives thereof; and any combination thereof, and/or
Or chain extenders and/or crosslinkers, such as peroxide, amine or acrylic functional chain extenders, and/or
-lubricants, including stearates, such as calcium stearate and magnesium stearate; and natural waxes such as palm wax, soybean wax, beeswax, sugarcane wax, tapioca wax, candelilla wax, rice bran wax, strawberry wax, bayberry wax, and month Gui La; or any mixture thereof.
15. The method according to any of the preceding claims, wherein the extrusion is performed at a temperature above the melting temperature of the polyester blend, preferably at a temperature of at least 190 ℃, such as at about 200 ℃.
16. A method according to any one of the preceding claims, wherein the mixture is compounded in twin screw extrusion.
17. A method according to claim 16, wherein the screw speed in the extrusion is in the range of 50 to 350rpm, such as 150rpm.
18. A method according to any one of the preceding claims, wherein the mixture is compounded in the extrusion into strands which are cooled in a water bath and finally granulated into granules.
19. A biobased silane modified polyester composition obtainable by the process according to any one of the preceding claims.
20. Use of the composition according to claim 19 as packaging material.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20206213 | 2020-11-27 | ||
| EP20397514.9 | 2020-11-27 | ||
| FI20206213 | 2020-11-27 | ||
| PCT/FI2021/050818 WO2022112660A1 (en) | 2020-11-27 | 2021-11-26 | Silane modified polyester composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116507661A true CN116507661A (en) | 2023-07-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180078281.0A Pending CN116507661A (en) | 2020-11-27 | 2021-11-26 | Silane modified polyester composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117863697A (en) * | 2024-03-11 | 2024-04-12 | 衢州聚瑞新材料科技有限公司 | High-barrier biodegradable bubble film and preparation method thereof |
-
2021
- 2021-11-26 CN CN202180078281.0A patent/CN116507661A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117863697A (en) * | 2024-03-11 | 2024-04-12 | 衢州聚瑞新材料科技有限公司 | High-barrier biodegradable bubble film and preparation method thereof |
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