DE2703417A1 - FELT ADHESIVE BASED ON SATURATED POLYESTER - Google Patents
FELT ADHESIVE BASED ON SATURATED POLYESTERInfo
- Publication number
- DE2703417A1 DE2703417A1 DE19772703417 DE2703417A DE2703417A1 DE 2703417 A1 DE2703417 A1 DE 2703417A1 DE 19772703417 DE19772703417 DE 19772703417 DE 2703417 A DE2703417 A DE 2703417A DE 2703417 A1 DE2703417 A1 DE 2703417A1
- Authority
- DE
- Germany
- Prior art keywords
- polyester
- phosphite
- saturated polyester
- adhesive based
- melt adhesives
- 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.)
- Withdrawn
Links
- 229920000728 polyester Polymers 0.000 title claims description 19
- 229920006395 saturated elastomer Polymers 0.000 title description 6
- 239000000853 adhesive Substances 0.000 title description 4
- 230000001070 adhesive effect Effects 0.000 title description 4
- 239000004831 Hot glue Substances 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MIOMYULHSNSWBW-UHFFFAOYSA-N (2,3,4-tridodecylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCCCCC)=C1CCCCCCCCCCCC MIOMYULHSNSWBW-UHFFFAOYSA-N 0.000 description 1
- BODXZBYILNTHRT-UHFFFAOYSA-N (2,3,4-tritert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1C(C)(C)C BODXZBYILNTHRT-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- MBTUMDUTYXDWKT-UHFFFAOYSA-N 2-phenylethyl dihydrogen phosphite Chemical compound OP(O)OCCC1=CC=CC=C1 MBTUMDUTYXDWKT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- TUOQCIYKPUYVJW-UHFFFAOYSA-N dibutyl phenyl phosphite Chemical compound CCCCOP(OCCCC)OC1=CC=CC=C1 TUOQCIYKPUYVJW-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HEGXHCKAUFQNPC-UHFFFAOYSA-N dicyclohexyl hydrogen phosphite Chemical compound C1CCCCC1OP(O)OC1CCCCC1 HEGXHCKAUFQNPC-UHFFFAOYSA-N 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- JYZMHBGJHAWIME-UHFFFAOYSA-N dihydrogen phosphate;trimethylazanium Chemical compound CN(C)C.OP(O)(O)=O JYZMHBGJHAWIME-UHFFFAOYSA-N 0.000 description 1
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- KIMPPGSMONZDMN-UHFFFAOYSA-N sodium;dihydrogen phosphite Chemical compound [Na+].OP(O)[O-] KIMPPGSMONZDMN-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
- C08L2666/40—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
BASF Aktiengesellschaft . /n<L· ιΊ BASF Aktiengesellschaft. / n <L · ιΊ
Unser Zeichen; Q.Z. 32 ^02 V/d/Br C>700 Ludv/igshafen, 25.01.1977 Our sign; QZ 32 ^ 02 V / d / Br C> 700 Ludv / igshafen, January 25, 1977
Als Schmelzkleber werden in steigendem Umfang thermoplastisch verarbeitbare Polymere, z.B. Polyviny!verbindungen, synthetische Polyamide sowie gesättigte lineare Copolyester eingesetzt.As hot melt adhesives, thermoplastically processable adhesives are becoming increasingly popular Polymers, e.g. polyvinyl compounds, synthetic polyamides and saturated linear copolyesters are used.
Besonders für die Verklebung von Leder, Kunstleder u.a. Materialien sind schon lineare, gesättigte Copolyester auf der Basis aromatischer und/oder aliphatischer Dicarbonsäuren sowie von aliphatischen Glykolen bekannt geworden. Schmelzkleber dieser Art sind z.B. in der deutschen Patentschrift 1 103 ^89, der britischen Patentschrift 813 212, den belgischen Patentschriften 557 309 und 7^7 199 sowie der französischen Patentschrift 1 179 399 beschrieben. Es ist außerdem schon lange allgemein bekannt, durch Zusätze eines anorganischen, in den Polymeren praktisch unlöslichen feinvertoilten Pulvers in geringer Konzentration die Kristallisationsgeschwindigkeit und damit die Erstarrungsgeschwindigkeit erheblich zu beschleunigen.Especially for the bonding of leather, artificial leather and other materials are linear, saturated copolyesters based on aromatic and / or aliphatic dicarboxylic acids as well as aliphatic ones Glycols became known. Hot melt adhesives of this type are, for example, in German Patent 1 103 ^ 89, British Patent specification 813 212, the Belgian patent specifications 557 309 and 7 ^ 7 199 and the French patent specification 1,179,399. It has also long been generally known that it can be finely dispersed through the addition of an inorganic, practically insoluble in the polymers Powder in low concentration increases the rate of crystallization and thus the rate of solidification considerably to accelerate.
Die bisher als Schmelzkleber praktisch eingesetzten Copolyester bestehen nun entweder aus mindestens h Komponenten oder aus Genischen von verschiedenen Copolyestern, und ihre Erstarrungsgeschwindigkeit läßt im allgemeinen zu wünschen übrig. Wegen dttr verhältnismäßig komplizierten Ausgangsgemische sind diese Produkte im allgemeinen nicht ohne weiteres in konventionellen Polyesteranlagen mit ausreichend hohen Polymerisationsgraden erhältlich, und ihre Eigenschaften sind nicht immer ausreichend reproduzierbar. Ein weiterer Nachteil der bekannten Schmelzkleber auf Basis von gesättigten Polyestern ist ihr schlechtes Fostigkeitsverhalten, d.h. sie zeigen bei geringer Klebefestigkeit nur eine niedrige Bruchdehnung der Verbindungsstellen. Es treten bei den bekannten Schmelzklebern auf Basis gesättigter Polyester auch unerwünschte Verfärbungen auf.The copolyesters previously used in practice as hot-melt adhesives now consist either of at least h components or of mixtures of different copolyesters, and their rate of solidification generally leaves something to be desired. Because of the relatively complicated starting mixtures, these products are generally not readily available in conventional polyester plants with sufficiently high degrees of polymerization, and their properties are not always sufficiently reproducible. A further disadvantage of the known hot-melt adhesives based on saturated polyesters is their poor strength behavior, ie they show only a low elongation at break at the connection points with low adhesive strength. In the case of the known hot-melt adhesives based on saturated polyester, undesirable discoloration also occurs.
809831/0132 _ 2 _809831/0132 _ 2 _
11 B/76 -- -Ζ-:- ' 11 B / 76 - -Ζ -: - '
O. Z. 32 402O. Z. 32 402
Es v/urde nun gefunden, dan Schnelzkleber aus einem Polyester aus 10 - 40 Mol.-^ Adipinsäure, 60 - 70 Hol.-;* Terephthalsäure und einem 2-6 C-Atome enthaltenden Alkandiol, die (a) 0,05 bis 0,5 Gewichtsprozent, bezogen auf den Polyester, an Talkum und (b) 0,05 bis 0,5 Gewichtsprozent, bezogen auf den Polyester, eines Esters oder Salzes einer Phosphors/Lure enthalten, ein besonders gutes Festigkeitsverhalten und praktisch keine Neigungen zu Verfärbungen zeigen. Ein v/eiterer Vorteil der neuen Schmelzkleber ist, daß sie mit ausreichend hohen Polykondensationsgraden leicht in konventionellen Polyesteranlagen hergestellt werden können. Die für die neuen Schmelzkleber verwendeten Polyester enthalten vorzugsweise 20 35 Mol.-^ Adipinsäure und 80 - 65 \\o\.-% Terephthalsäure sowie lineare, 2-6 C-Atome enthaltende Alkandiole mit endständigen OH-Gruppen einkondensiert. Von besonderem Interesse sind Polyester, die als Alkandiol 1,^-Butandiol einkondensiert enthalten. Andere geeignete Alkandiole sind 1,2-Äthylenclykol, 1,3-Propandiol und 1,6-IIexandiol.It has now been found that a high-speed adhesive made from a polyester composed of 10-40 mol .- ^ adipic acid, 60-70 hol .-; * terephthalic acid and an alkanediol containing 2-6 carbon atoms, which (a) 0.05 to 0.5 weight percent, based on the polyester, of talc, and (b) 0.05 to 0.5 weight percent, based o n the polyester, an ester or a salt containing a particularly good strength behavior phosphorus / Lure and virtually no tendencies to Show discoloration. Another advantage of the new hot-melt adhesives is that they can easily be produced in conventional polyester plants with a sufficiently high degree of polycondensation. The polyesters used for the new hot-melt adhesives preferably contain 20-35 mol .- ^ adipic acid and 80-65 \\ o \ .-% terephthalic acid and linear alkanediols containing 2-6 carbon atoms with terminal OH groups condensed in. Of particular interest are polyesters which contain 1, ^ - butanediol as alkanediol in condensed form. Other suitable alkanediols are 1,2-ethylene glycol, 1,3-propanediol and 1,6-IIexanediol.
Die; Polyester können in an sich bekannter V/eise aus den Dicarbonsäuren oder deren Derivaten, z.B. deren Dialkylestern niederer Alkohole, insbesondere deren Methylester, durch Umsetzen mit dan Alkandiolen und unter Zusatz der üblichen Katalysatoren durch Polykondensation hergestellt werden und haben im allgemeinen sine Grenzviskosität von 0,36 - 1,93, insbesondere von 0,53 - 0,96, gemessen in 0,5 pißer Lösung in einem Gemisch aus o-Dichlorbonzol und Phenol (Gewichtsverhältnis 2:3) bei 25°C. Die Polyester können auch in an sich bekannter V/eise durch Mischpolykondensation der Alkandiolester der Terephthalsäure und der Adipinsäure hergestellt sein.The; Polyesters can be prepared from the dicarboxylic acids in a manner known per se or their derivatives, e.g. their dialkyl esters of lower alcohols, in particular their methyl esters, by reaction with dan Alkanediols and are prepared by polycondensation with the addition of the usual catalysts and generally have sine Intrinsic viscosity of 0.36-1.93, in particular 0.53-0.96, measured in a 0.5 piss solution in a mixture of o-dichlorobonzene and phenol (weight ratio 2: 3) at 25 ° C. The polyesters can also be prepared in a manner known per se by mixed polycondensation the alkanediol esters of terephthalic acid and adipic acid.
Das in den neuen Schmelzklebern enthaltene Talkum kann während oder nach der Polykondensation zu dem Polyester gegeben werden und hat vorzugsweise eine Teilchengröße unter lO.um, insbesondere von 1 bis 5/Um.The talc contained in the new hot melt adhesives can be added to the polyester during or after the polycondensation and preferably has a particle size below 10 µm, in particular from 1 to 5 / um.
809831/0132 ORiGiNAL /NSPECTED809831/0132 ORiGiNAL / NSPECTED
O. Z. 52 402O. Z. 52 402
2703ΑΊ72703ΑΊ7
Als Derivate von Phosphorsäuren, die in den Schmelzklebern enthalten sind, seien beispielsweise Natriumdihydrogenphosphat, Natriumdihydrogenphosphit, Ammoniumdihydrogenphosphat, Trimethylammonium-dihydrogenphosphat sowie Natriumsalze von Polyphosphorsäuren (z.B. Calgon) genannt. Geeignete Ester von Phosphorsäure sind Phosphite und Phosphate aliphatischer und/oder aromatischer Alkohole oder von Phenolen. Genannt seien z.B. Triphenylphosphit, Triphenylphosphat, Tris-nonylphenyl-phosphit, Tris-dodecylphenylphosphit, Tris-undocylphenyl-phosphit, Tris-nonylphenyl-phosphat, Triisopropylphosphit, Tris-tertiärbutylphenylphosphit, Trimethylphosphat, Glykolphosphat, Phenyläthylphosphit, Dibutylphenylphosphit, Dicyclohexylhydrogenphosphit und Diphenyläthylphosphat. Von besonderem Interesse sind Phenolester der phosphorigen Säure, wie insbesondere Triphenylphosphit.As derivatives of phosphoric acids contained in hot melt adhesives are, for example, sodium dihydrogen phosphate, Sodium dihydrogen phosphite, ammonium dihydrogen phosphate, trimethylammonium dihydrogen phosphate as well as sodium salts of polyphosphoric acids (e.g. Calgon). Suitable esters of phosphoric acid are phosphites and phosphates of aliphatic and / or aromatic alcohols or of phenols. Examples include triphenyl phosphite, Triphenyl phosphate, tris-nonylphenyl phosphite, tris-dodecylphenyl phosphite, Tris-undocylphenyl-phosphite, tris-nonylphenyl-phosphate, Triisopropyl phosphite, tris-tertiary butylphenyl phosphite, trimethyl phosphate, Glycol phosphate, phenylethyl phosphite, dibutylphenyl phosphite, Dicyclohexyl hydrogen phosphite and diphenyl ethyl phosphate. Of special Phenol esters of phosphorous acid, such as triphenyl phosphite in particular, are of interest.
Für die Herstellung der Schmelzkleber haben sich solche Polyester besonders bewährt, zu deren Herstellung als Katalysatoren Alkyltitansäureester, wie besonders Tetrabutylorthotitanat eingesetzt wurden. Die neuen Schmelzkleber eignen sich insbesondere zum Verkleben von Leder und können mit Vorteil bei der Herstellung von Schuhen eingesetzt werden.For the production of hot melt adhesives such polyesters have proven to be particularly useful, for their production as catalysts, alkyltitanic acid esters, how especially tetrabutyl orthotitanate were used. The new hot melt adhesives are particularly suitable for gluing of leather and can be used to advantage in the manufacture of shoes.
Die im folgenden Beispiel angegebenen Teile sind Gewichtsteile.The parts given in the following example are parts by weight.
In einem beheizten Rührkessel mit aufgesetzter Kolonne werden 97 Teile Terephthalsäuredimethylester und 68 Teile Butandiol-l,^ unter Rühren auf I1IO0C aufgeheizt. In die homogene Schmelze werden allmählich 0,1 Teile Tetrabutylorthotitanat eingetragen und die Temperatur des Reaktionsgemisches im Verlauf von 2 Stunden unter gleichzeitigem Rühren bis 23O°C erhöht. Das freiwerdende Methanol wird über die Kolonne abdestilliert. Nach beendeter Umesterung werden in die Schmelze unter Rühren bei 230° und Normaldruck 22 Teile Adipinsäure eingetragen und das Gemisch bis zur Entfernung der berechneten Menge Wasser gerührt. Danach werden dem Ansatz 0,1 Teile Triphenylphosphit und 0,1 Teile Talkum (Korn-In a heated stirred vessel with fitted column, 97 parts of dimethyl terephthalate and 68 parts of butane-l, ^ heated with stirring to I 1 0 C IO. 0.1 part of tetrabutyl orthotitanate is gradually introduced into the homogeneous melt and the temperature of the reaction mixture is increased to 230 ° C. over the course of 2 hours while stirring at the same time. The methanol released is distilled off through the column. When the transesterification has ended, 22 parts of adipic acid are introduced into the melt with stirring at 230 ° and normal pressure and the mixture is stirred until the calculated amount of water has been removed. Then 0.1 part of triphenyl phosphite and 0.1 part of talc (grain
809831/0132809831/0132
- jt- O.Z. 32 402- jt- O.Z. 32 402
27U34I727U34I7
größe 10.um) zugesetzt und die; Schnelzü innerhalb einer Stunde unter Rühren und gleichzeitigem Evakuieren auf v/eniger als 1 Torr auf 245 - 25O°C erhitzt und in diesem Temperaturbereich bis zum Erreichen des gewünschten Polykondensationsgrades (etwa 2 bis 3 Stunden) nachkondensiert. Man erhält ein farbloses Folykondensat der Grenzviskosität 0,73 (gemessen in einem Gemisch o-Dichlorbonzol/Phenol 2 : 3, 0,5 % bei 25°C) und des (differential-thermoanalytisch bestimmten) Schmelzpunkts 175°C.size 10.um) added and the; Quickly heated within one hour with stirring and simultaneous evacuation to less than 1 Torr to 245-25O ° C and post-condensed in this temperature range until the desired degree of polycondensation (about 2 to 3 hours). A colorless poly-condensate with an intrinsic viscosity of 0.73 (measured in a mixture of o-dichlorobonzene / phenol 2: 3, 0.5 % at 25 ° C.) and a melting point of 175 ° C. (determined by differential thermal analysis) is obtained.
Aus dem erhaltenen Schmelzkleber wird ein Film von 0,5 mm Stärke geformt und die mechanischen Eigenschaften bestimmt. Es ergeben sich folgende Werte:A film 0.5 mm thick is formed from the hot melt adhesive obtained and the mechanical properties are determined. It surrendered the following values:
Biegefestigkeit 22 N/mm2 Bruchdehnung 90 % undFlexural strength 22 N / mm 2 elongation at break 90 % and
Knickbruchzahl I300Buckling fracture number I300
(90° Knickwinkel,
Anzahl der Biegungen
bis zum Bruch)(90 ° articulation angle,
Number of bends
until break)
In einem beheizten Rührkessel mit aufgesetzter Kolonne werden 155 Teile Terephthalsäuredimethylester 38,8 Teile Isophthalsäure, 135 Teile Butandiol-1,4, 7,44 . 10"3 Teile Zinkacetat und 15 »5 * 10"-5TeUe Tetrabutylorthotitanat eingetragen und unter Stickstoff unter Rühren auf I80 bis 22O°C erhitzt. Das freiwerdende Methanol wird über die Kolonne abdestilliert. Danach setzt man 0,2 Teile Triphenylphosphit und 0,2 Teile Talkum (Korngröße 10,Um) zu und steigert die Temperatur bis auf 25O°C. Unter Druckverminderung auf 1 Torr erhöht man die Temperatur innerhalb einer Stunde auf 27O°C. Unter diesen Bedingungen wird noch etwa 1 Stunde gerührt bis der gewünschte Polykondensationsgrad erreicht ist. Man erhält einen Polyester der Grenzviskosität 0,73 (gemessen in einem Gemisch von o-Dichlorbenzol/Phenol =2:3 bei 25°C).In a heated stirred tank with an attached column, 155 parts of dimethyl terephthalate, 38.8 parts of isophthalic acid, 135 parts of 1,4-butanediol, 7.44 are added. 10 "3 parts of zinc acetate and 15» 5 10 * "- entered 5 TeUe tetrabutyl orthotitanate and heated under nitrogen with stirring to I80 to 22O ° C. The methanol released is distilled off through the column. Then 0.2 part of triphenyl phosphite and 0.2 part of talc (grain size 10 μm) are added and the temperature is increased to 250.degree. While reducing the pressure to 1 Torr, the temperature is increased to 270 ° C. over the course of one hour. Under these conditions, stirring is continued for about 1 hour until the desired degree of polycondensation is reached. A polyester with an intrinsic viscosity of 0.73 is obtained (measured in a mixture of o-dichlorobenzene / phenol = 2: 3 at 25 ° C.).
809831/0132809831/0132
( O. Z. 32 ( OZ 32
Aus dem Geschmolzenen Produkt viird ein Film von 0,5 mm Stärke gefornt und die mechanischen Eigenschaften bestimmt. Es ergeben sich folgende Werte:A film 0.5 mm thick is made from the molten product shaped and the mechanical properties determined. The following values result:
ρ Biegeestigkoit < 5 N/mm ,ρ flexural strength < 5 N / mm,
Bruchdehnung <Z 5 % undElongation at break <Z 5% and
Knickbruchzahl 1 (Bruch nach dem ersten Knick)Buckling break number 1 (break after the first break)
(90° Knickwinkel, Anzahl der Biegungen bis zun Bruch)(90 ° kink angle, number of bends until break)
809831/0132809831/0132
Claims (1)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772703417 DE2703417A1 (en) | 1977-01-28 | 1977-01-28 | FELT ADHESIVE BASED ON SATURATED POLYESTER |
| CA294,690A CA1091838A (en) | 1977-01-28 | 1978-01-10 | Hot-melt adhesive based on a saturated polyester |
| JP342778A JPS5396043A (en) | 1977-01-28 | 1978-01-18 | Hot melt adhesives based on saturated polyesters |
| IT47804/78A IT1104144B (en) | 1977-01-28 | 1978-01-26 | ADHESIVE FOR MELTING BASED ON SATURATED POLYESTERS |
| FR7802358A FR2378838A1 (en) | 1977-01-28 | 1978-01-27 | FUSABLE GLUES BASED ON SATURATED POLYESTERS |
| GB3339/78A GB1593340A (en) | 1977-01-28 | 1978-01-27 | Hot-melt adhesive based on a saturated polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772703417 DE2703417A1 (en) | 1977-01-28 | 1977-01-28 | FELT ADHESIVE BASED ON SATURATED POLYESTER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2703417A1 true DE2703417A1 (en) | 1978-08-03 |
Family
ID=5999723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19772703417 Withdrawn DE2703417A1 (en) | 1977-01-28 | 1977-01-28 | FELT ADHESIVE BASED ON SATURATED POLYESTER |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5396043A (en) |
| CA (1) | CA1091838A (en) |
| DE (1) | DE2703417A1 (en) |
| FR (1) | FR2378838A1 (en) |
| GB (1) | GB1593340A (en) |
| IT (1) | IT1104144B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2945729A1 (en) * | 1979-11-13 | 1981-05-21 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR PRODUCING HIGH MOLECULAR, LINEAR POLYESTERS |
| US5446079A (en) * | 1990-11-30 | 1995-08-29 | Eastman Chemical Company | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9607302D0 (en) * | 1996-04-09 | 1996-06-12 | British United Shoe Machinery | Shoe material |
| CN110452653B (en) * | 2019-07-29 | 2021-09-07 | 广东莱尔新材料科技股份有限公司 | High-viscosity weather-resistant hot melt adhesive, preparation method thereof and hot melt adhesive film |
-
1977
- 1977-01-28 DE DE19772703417 patent/DE2703417A1/en not_active Withdrawn
-
1978
- 1978-01-10 CA CA294,690A patent/CA1091838A/en not_active Expired
- 1978-01-18 JP JP342778A patent/JPS5396043A/en active Pending
- 1978-01-26 IT IT47804/78A patent/IT1104144B/en active
- 1978-01-27 FR FR7802358A patent/FR2378838A1/en active Granted
- 1978-01-27 GB GB3339/78A patent/GB1593340A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2945729A1 (en) * | 1979-11-13 | 1981-05-21 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR PRODUCING HIGH MOLECULAR, LINEAR POLYESTERS |
| US5446079A (en) * | 1990-11-30 | 1995-08-29 | Eastman Chemical Company | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
| US5580911A (en) * | 1990-11-30 | 1996-12-03 | Eastman Chemical Company | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
| US5599858A (en) * | 1990-11-30 | 1997-02-04 | Eastman Chemical Company | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1593340A (en) | 1981-07-15 |
| FR2378838B1 (en) | 1980-08-29 |
| JPS5396043A (en) | 1978-08-22 |
| CA1091838A (en) | 1980-12-16 |
| IT1104144B (en) | 1985-10-14 |
| FR2378838A1 (en) | 1978-08-25 |
| IT7847804A0 (en) | 1978-01-26 |
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