[go: up one dir, main page]

EP0000927A1 - Procédé pour la stabilisation de polyesteruréthanes thermoplastiques - Google Patents

Procédé pour la stabilisation de polyesteruréthanes thermoplastiques Download PDF

Info

Publication number
EP0000927A1
EP0000927A1 EP78100689A EP78100689A EP0000927A1 EP 0000927 A1 EP0000927 A1 EP 0000927A1 EP 78100689 A EP78100689 A EP 78100689A EP 78100689 A EP78100689 A EP 78100689A EP 0000927 A1 EP0000927 A1 EP 0000927A1
Authority
EP
European Patent Office
Prior art keywords
polyesterurethane
stabilized
acid
diisocyanate
diamine
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.)
Granted
Application number
EP78100689A
Other languages
German (de)
English (en)
Other versions
EP0000927B1 (fr
Inventor
Herbert L. Heiss
Robert P. Yeater
Russell P. Jr. Carter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Corp
Original Assignee
Mobay Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mobay Corp filed Critical Mobay Corp
Publication of EP0000927A1 publication Critical patent/EP0000927A1/fr
Application granted granted Critical
Publication of EP0000927B1 publication Critical patent/EP0000927B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring

Definitions

  • thermoplastic polyurethanes based on polyesters will ultimately discolor, only mild interest has been displayed in the past in providing products with low initial color. Whenever possible, care was taken to minimize color of the reactants, but to date, the thermoplastic polyesterurethanes themselves have not been assigned any color specifications. Recently, there has developed a market for colorless, transparent roller skate wheels molded from thermoplastic polyurethanes.
  • the specific type of discoloration involved is that which occurred during exposure of the thermoplastic polyesterurethane to processing temperatures experienced during drying, extrusion or molding. The yellowing of the polymer did not seem to be associated with any significant change in strength properties and was entirely different from the discoloration which occurs during the service life of the ultimate product (i.e. weathering). It was found that this discoloration could occur during pelletization extrusion, resulting in the shipment of pellets which varied in color. It was also found that some lots of polymer discolored even more during the final product processing with the result that the final product also varied in color.
  • thermoplastic polyurethanes before, during or after the polymer-forming reaction, small amounts of 2-oxazolidones. Additionally, and quite unexpectedly, the oxazolidones described herein, when added to the thermoplastic polyurethane are effective color stabilizers.
  • the preferred 2-oxazolidones are generally known and correspond to the formula: where R represents hydrogen or an organic radical which is free of epoxide reactable groups, such as an aliphatic, aromatic, mixed aliphatic-aromatic, or an organic polymer radical; X 1 and X 2 may be the same or different and represent hydrogen or organic radicals which are free of epoxide reactive groups; and n represents an integer of 1 to 3.
  • R represents hydrogen or an organic radical which is free of epoxide reactable groups, such as an aliphatic, aromatic, mixed aliphatic-aromatic, or an organic polymer radical
  • X 1 and X 2 may be the same or different and represent hydrogen or organic radicals which are free of epoxide reactive groups
  • n represents an integer of 1 to 3.
  • these oxazolidones may be produced in a number of ways, e.g.
  • R, X 1 and X 2 each represent a hydrogen atom or a radical selected from the group consisting of alkyl and cycloalkyl of from 1 to 12 carbon atoms and aryl, aralkyl and alkylaryl of from 6 to 15 carbon atoms and n represents an integer of from 1 to 3. It is preferable that X 1 and X 2 each represent hydrogen.
  • 2-oxazolidones useful in the instant invention are generally known and have been described, e.g., in United States Patents 2,977,369; 2,977,370; 2,977,371; and 4,022,721 and in "HETEROCYCLIC COMPOUNDS", VOLUME 5, "Five-Membered Heterocycles Containing Two Hetero Atoms and Their Benzo-Derivatives", edited by Robert C. Elderfield, 1957, pages 396 through 402, the disclosures of which are herein incorporated by reference.
  • the oxazolidones should be added to the thermoplastic polyurethanes in amounts effective to stabilize the polyurethane and preferably in amounts ranging from 0.02 to 6 percent by weight based on the total weight of the polyurethane. It has been surprisingly found that when these amounts are used, in addition to improved stability against processing discoloration, the polyurethanes exhibit greatly improved hydrolytic stability.
  • the oxazolidone can be added to the polyester, the organic isocyanate or other reactants used in the preparation of the polyesterurethane, such as a chain extender, or it may be added to the polyesterurethane product. Addition to the product itself is generally most practical. The addition can be made in the dissolved state, by extruding, milling, stirring or any suitable technique.
  • any suitable polyester may be used, such as those prepared from polycarboxylic acids and polyhydric alcohols.
  • Any suitable polycarboxylic acid may be used such as, for example, benzene tricarboxylic acid, adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid. pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, thiodipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid and the like.
  • Any suitable polyhydric alcohol may be used such as, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, bis-(hydroxy methyl cyclohexane), diethylene glycol, 2,2'-dimethyl propylene glycol, 1,3,6-hexanetriol, trimethylol propane, pentaerythritol, sorbitol, glycerine and the like.
  • polyesters in the preparation of polyesterurethanes are those prepared from lactams, lactones and the like.
  • polyesteramides an amine is included in the reaction of a carboxylic acid and an alcohol, or an aminoalcohol or aminoacid is used.
  • Any suitable amino compound can be used to prepare polyesteramides such as, for example, hexamethylene diamine, ethylene diamine, propylene diamine, butylene diamine, cyclohexyl diamine, phenylene diamine, tolylene diamine, xylylene diamine, 4,4'-diamino-diphenyl-methane, naphthylene diamine, aminoethyl alcohol, aminopropyl alcohol, aminobutyl alcohol, aminobenzyl alcohol, aminoacetic acid, aminopropionic acid, aminobutyric acid, aminovaleric acid, aminophthalic acid, aminobenzoic acid and the like.
  • the amino compounds may be reacted either simultaneously with the ester forming components or sequentially therewith.
  • Any suitable polyisocyanate can be used in the preparation of polyesterurethanes by reaction with a polyester such as, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,5-tolylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 1-methyl-3,5-diethyl-2,6-phenylene diisocyanate, 1,3,5-triethyl-2,4-phenylene diisocyanate, 1-,ethyl-3,5-diethyl-6-chloro-2,4-phenylene diisocyanate, 6-methyl-2,4-
  • the invention is particularly applicable to the stabilization of p ol y esterurethanes used in the manufacture of elastomers or casting resins for molded elements.
  • any of the above-mentioned polyesters may be reacted with any of the isocyanates set forth and a chain extending agent containing active hydrogen atoms which are reactive with NCO groups and having a molecular weight less than about 500 such as, for example, water, ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, butenediol, butynediol, xylylene glycol, amylene glycol, neopentyl glycol, 2,3-butanediol, 1,4-phenylene-bis-(B-hydroxy ethyl ether), 1,3-phenylene-bis-(3-hydroxy ethyl ether), bis-(hydroxy methylcyclohexane), hexanediol, diethylene glycol, dipropylene glycol and the like; polyamines such as, for example, ethylene diamine,
  • polyester polyol prepared from 1,4-butanediol and adipic acid having a molecular weight of about 2,000 and a hvdroxyl number of 56
  • methylene bis-phenylisocyanate
  • 1,4-butane diol 1,4-butane diol
  • the oxazolidones specified in the Table were added to the granulates in the amounts specified based on the weight of the product.
  • the resultant mixture was divided into two portions, one was strand pelletized and one was injection molded into slabs.
  • the pellets were placed in ovens and heated for 16 hours at 110° to develop color, after which they were rated for color stability on a scale of 1 to 10, 1 being colorless and 10 being most discolored.
  • the molded portions were aged at 100 % relative humidity at 100 0 C for 2 days to cause hydrolytic decomposition, after which they were dried and tested. The percent tensile strength retained compared to the original value was used to measure the hydrolytic stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP78100689A 1977-08-26 1978-08-17 Procédé pour la stabilisation de polyesteruréthanes thermoplastiques Expired EP0000927B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/828,120 US4123419A (en) 1977-08-26 1977-08-26 Stabilized thermoplastic polyesterurethanes
US828120 1986-02-10

Publications (2)

Publication Number Publication Date
EP0000927A1 true EP0000927A1 (fr) 1979-03-07
EP0000927B1 EP0000927B1 (fr) 1981-08-26

Family

ID=25250967

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100689A Expired EP0000927B1 (fr) 1977-08-26 1978-08-17 Procédé pour la stabilisation de polyesteruréthanes thermoplastiques

Country Status (4)

Country Link
US (1) US4123419A (fr)
EP (1) EP0000927B1 (fr)
CA (1) CA1081894A (fr)
DE (1) DE2860982D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993005109A1 (fr) * 1991-09-05 1993-03-18 Minnesota Mining And Manufacturing Company Preparation de compositions de polyurethanes

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0694500B2 (ja) * 1987-10-02 1994-11-24 ポリプラスチックス株式会社 難燃性改良成形用熱可塑性ポリエステル樹脂の製造法
DE19807502B4 (de) 1998-02-21 2004-04-08 Basf Ag Verfahren zur Nachvernetzung von Hydrogelen mit 2-Oxazolidinonen, daraus hergestellte Hydrogele und deren Verwendung
US6503979B1 (en) * 1998-02-26 2003-01-07 Basf Aktiengesellschaft Method for cross-linking hydrogels with bis- and poly-2-oxazolidinones
JP2014533752A (ja) 2011-11-17 2014-12-15 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 重縮合物を加水分解安定化するための添加剤

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4420247B1 (fr) * 1967-03-10 1969-09-01
GB1453694A (en) * 1972-08-25 1976-10-27 Shoe & Allied Trades Res Ass Stabilization of polymeric materials against hydrolysis

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2885420A (en) * 1956-01-27 1959-05-05 Du Pont Stabilization of organic isocyanates
US3020262A (en) * 1957-12-19 1962-02-06 Jefferson Chem Co Inc Method for producing 2-oxazolidones from epoxides and isocyanates
US3334110A (en) * 1965-08-16 1967-08-01 Baker Chem Co J T Method for preparing epoxyoxazolidinones
US3471442A (en) * 1967-02-02 1969-10-07 American Cyanamid Co Process for the preparation of thermoplastic polymers prepared by reacting diepoxide monomers with aromatic diisocyanates
US3817938A (en) * 1971-02-12 1974-06-18 K Ashida Polyoxazolidone catalyst
JPS5133905B2 (fr) * 1972-04-14 1976-09-22
US3781229A (en) * 1972-10-31 1973-12-25 Gen Electric Storage stable premix for production of polyurethane foam
US4022721A (en) * 1974-09-26 1977-05-10 Mitsubishi Chemical Industries Ltd. Process for producing compounds having an oxazolidone ring using a complex of aluminum halide catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4420247B1 (fr) * 1967-03-10 1969-09-01
GB1453694A (en) * 1972-08-25 1976-10-27 Shoe & Allied Trades Res Ass Stabilization of polymeric materials against hydrolysis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 72, Febr. 9, 1970, nr. 22527r; & JP-B-44 020 247 (SHIMIZU, TOSHIO et al.) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993005109A1 (fr) * 1991-09-05 1993-03-18 Minnesota Mining And Manufacturing Company Preparation de compositions de polyurethanes

Also Published As

Publication number Publication date
DE2860982D1 (en) 1981-11-19
CA1081894A (fr) 1980-07-15
US4123419A (en) 1978-10-31
EP0000927B1 (fr) 1981-08-26

Similar Documents

Publication Publication Date Title
US4297472A (en) Method of producing color stable thermoplastic polymethanes and products made thereby
US5210170A (en) Process for stabilizing plastics containing ester groups
US3193523A (en) Stabilization of polyesters with substituted carbodiimides
KR100461621B1 (ko) 폴리우레탄수지
GB1559031A (en) Permanently stabilizes polyurethanes
US3193525A (en) Polyurethane polymers
US3401144A (en) Stabilized polyesterurethanes
US3919166A (en) Fire retardant polyurethanes and polyurea-urethanes having improved processability and color stability
US4088629A (en) Stabilization of synthetic polymers
US4123419A (en) Stabilized thermoplastic polyesterurethanes
US3226368A (en) Process of preparing polyesterurethanes containing carbodiimide groups
US3485778A (en) Stabilization of polyurethane synthetic resins
JP2625508B2 (ja) 安定化されたポリウレタン
US3536663A (en) Stabilized polyurethanes
JP3333252B2 (ja) ジフェニルメタンジイソシアネート系化合物の着色防止法
USRE30721E (en) Stabilized thermoplastic polyesterurethanes
US3538046A (en) Polyurethanes stabilized with phenolic hydrazides
US3795638A (en) Stabilized polyurethane compositions
US5132387A (en) Hindered amine light stabilizer hydrazides for stabilizing polyurethane, polyurea and polyurethane-polyurea polymers
US3637583A (en) Polyesterurethanes stabilized with iminocarbonates
US3351608A (en) Stabilized polyurethanes
US3248454A (en) Storage stable polyurethanes with a di-4 aminophenyl methane derivative
EP0214292A1 (fr) Composition de stabilisation de polyurethane
JPS6029386B2 (ja) シアナミド類
US3475378A (en) Process for the production of high molecular weight polyurethane elastomers by the millable gum method

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed
AK Designated contracting states

Designated state(s): DE GB NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE GB NL

REF Corresponds to:

Ref document number: 2860982

Country of ref document: DE

Date of ref document: 19811119

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840724

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19870831

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19880817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19890301

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19890503

GBPC Gb: european patent ceased through non-payment of renewal fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT