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WO1991018944A1 - Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres - Google Patents

Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres Download PDF

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Publication number
WO1991018944A1
WO1991018944A1 PCT/US1990/003540 US9003540W WO9118944A1 WO 1991018944 A1 WO1991018944 A1 WO 1991018944A1 US 9003540 W US9003540 W US 9003540W WO 9118944 A1 WO9118944 A1 WO 9118944A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
photodegradation
tiθ2
anatase
composition
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.)
Ceased
Application number
PCT/US1990/003540
Other languages
English (en)
Inventor
Ronald P. Markovich
B. Alan Hdah
Dallas C. Pichnic
Gerald M. Lancaster
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Publication of WO1991018944A1 publication Critical patent/WO1991018944A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers

Definitions

  • the ethylene/carbon monoxide copolymers include those which have other copolymerizable monomers contained in the polymer, such as acrylic acid, methacrylic acid, vinyl alkylates, alkyl acrylates, and even minor amounts of lower olefins, such as propylene or butylene.
  • Patents showing the preferred method of making CO-containing ethylene copolymers include U.S. Patent 4,600,614 and U.S. Patent 4,601,948.
  • n is a plural number
  • R' is hydrogen or alkyl group
  • the photodegradation properties of olefin polymers which contain carbonyl groups along the chain are disclosed in U.S. Patent 3*676,401 and U.S. Patent 3,860,538.
  • HM88143 for a degradable polyethylene based white concentrate trademarked SPECTRATECHTM HM88143 by Quantum Chemical Corporation and described as 50 blend of polyethylene modified to be degradable and 50 of titanium dioxide (CAS RN: 13463-67-1); this Chemical Abstracts Service Registry Number is generic to Ti ⁇ 2-
  • Ti ⁇ 2 will accelerate the photodegradation of polyethylene and polypropylene.
  • the rutile form of Ti ⁇ 2 is relatively inactive with respect to the photodegradation of polymers to which it may be added, but it may be employed for other purposes, such as for pigmentation or thermal activity.
  • the term "polymers or copolymers” refers herein to portions of the photodegradating agents, and which are also useful in enhancing the photodegradation of the matrix resins.
  • a second aspect of the invention is a process of synergistically enhancing the photodegradation rate of photodegradation polymers containing carbonyl groups along the polymer chain; the said process comprising incorporating the anatase form of Ti ⁇ 2 therein.
  • copolymer containing copolymerized carbon monoxide (CO) in the polymer chain backbone is the preferred type of CO-containing polymer.
  • a process of providing a predetermined regulated rate of photodegradation to a matrix resin comprising blending the matrix resin with predetermined amounts of anatase Ti ⁇ 2, at least one CO- containing polymer and optionally rutile Ti ⁇ 2 > and/or a UV stabilizer.
  • additives and/or degradation accelerators and/or photostabilizers and/or photosensitizers may also be employed along with the agent of this invention either by way of having the photodegradation agent added to matrix resins which contain the said optional ingredients, or by way of adding the optional additives to matrix resins which contain the photodegradation agents, or by adding them to the matrix resin at substantially the same time.
  • the effect of the CO- containing polymer is not very likely to provide an appreciably significant effect on the photodegradation of the resin.
  • the polymer which contains the CO groups may not exhibit the physical properties needed for attaining the initial strength or other properties desired in the resin article of which it is to be a part.
  • a preferred range is 1 percent to 30 percent by weight, more preferably 2 percent to 20 percent by weight.
  • LLDPE linear low density polyethylene which is actually an ethylene/1-alkene copol ⁇ mer prepared by using a coordination catalyst, such as a Ziegler catalyst or the like.
  • MFR melt flow rate
  • MI melt index
  • LLDPE-1 Ethylene/octene copolymer, density of 0.941 g/cc and MFR of 4 g/10 min.
  • Ti ⁇ 2 Titanium oxide indicated as the anatase crystal form or the rutile crystal form, or in some instances it can be either one. Unless indicated otherwise, the Ti ⁇ 2 used is pigment grade Ti ⁇ 2 (particularly that available as Mobay ® Type A-X).
  • Example 2 In similar manner to Example 1, a composite blend is prepared consisting of 9.9 parts of LLDPE-1, 0.3 parts of LLDPE-2, 4.2 parts of ECO-2 and 0.6 parts
  • Example 2 In similar manner to Example 1, a composite blend is prepared consisting of 9.9 parts of LLDPE-1, 4.5 parts of LDPE-1 and 0.6 parts of Concentrate #4. The composite is tested by outside weathering and the
  • the range of about 1/99 to about 99/1 is believed to be operable, preferably about 40/60 to about 90/10, most preferably about 50/50 to about 80/20.
  • Ti ⁇ 2 acidic surface
  • ECO basic carbonyl
  • Ti ⁇ 2 can be either anatase or rutile or any variety having an acid surface.
  • Other particulate solid compounds having acid surfaces may be employed in place of, or along with, the Ti02 and the CO-containing olefin polymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Molding Of Porous Articles (AREA)
  • Epoxy Resins (AREA)

Abstract

Un mélange synergique de la forme anatase de TiO2 et d'un copolymère d'oléfine contenant du CO (en particulier de l'éthylène) offre un moyen avantageux d'améliorer et de réguler le taux de photodégradation de différents plastiques et de résines matriciels. Le mélange lui-même peut être utilisé directement pour la fabrication d'articles polymères, tels des films, des sacs, des emballages et objets analogues, ou il peut être utilisé comme un adjuvant (par exemple un adjuvant de lot principal) pour effectuer la photodégradation de polymères, de plastiques ou de résines matriciels. Il peut aussi comprendre d'autres adjuvants qui contribuent avantageusement à la régulation du taux de photodégration, tels que le TiO2 rutile et/ou d'autres matériaux stabilisant, absorbant ou sensibles aux rayons UV. En outre, la présence de TiO2 et d'un copolymère d'oléfine contenant du CO (en particulier l'éthylène) dans un autre polymère ou copolymère d'oléfine fournit une plage de température de thermosoudage plus étendue à l'autre polymère. N'importe laquelle des variétés de TiO2 peut être utilisée pour obtenir cet effet de plage de température de thermosoudage élargie si cette variété comporte des surfaces acides.
PCT/US1990/003540 1990-05-18 1990-06-21 Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres Ceased WO1991018944A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52526390A 1990-05-18 1990-05-18
US525,263 1990-05-18

Publications (1)

Publication Number Publication Date
WO1991018944A1 true WO1991018944A1 (fr) 1991-12-12

Family

ID=24092559

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/003540 Ceased WO1991018944A1 (fr) 1990-05-18 1990-06-21 Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres

Country Status (4)

Country Link
EP (1) EP0486524A4 (fr)
JP (1) JPH04504734A (fr)
AU (1) AU6148190A (fr)
WO (1) WO1991018944A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2061405A2 (es) * 1993-05-04 1994-12-01 Univ Granada Produccion de polihidroxialcanoatos (phas) por azotobacter chroococcum pha.
EP0669374A3 (fr) * 1994-02-25 1996-02-28 Bp Chem Int Ltd Mélanges de polymères.
WO1996006889A1 (fr) * 1994-08-26 1996-03-07 Bp Chemicals Limited Melanges de polycetone et de polyethylene basse densite a structure lineaire
WO2000031166A1 (fr) * 1998-11-19 2000-06-02 Uni Chem Co., Ltd. Film plastique bio-photodegradable, composition de charge plastique afferente et procede de preparation de cette composition
WO2011071843A1 (fr) * 2009-12-11 2011-06-16 Dow Global Technologies Llc Films photodégradables avec bonnes propriétés à la traction et à l'essai de résistance au choc au mouton
WO2014105608A1 (fr) 2012-12-28 2014-07-03 Dow Global Technologies Llc Polymères à base d'éthylène et leurs procédés de production
WO2015200426A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Polymères à base d'éthylène comprenant des motifs dérivés du monoxyde de carbone et d'un agent modifiant la rhéologie
WO2015200430A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Procédé pour préparer des polymères à base d'éthylène à l'aide d'une distribution de monoxyde de carbone
WO2017189299A1 (fr) 2016-04-29 2017-11-02 Dow Global Technologies Llc Compositions comprenant des copolymères d'éthylène-monoxyde de carbone
WO2019089750A1 (fr) 2017-10-31 2019-05-09 Dow Global Technologies Llc Interpolymères d'éthylène/co et procédés de fabrication associés

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352725A (en) * 1991-09-27 1994-10-04 Kerr-Mcgee Chemical Corporation Attenuation of polymer substrate degradation due to ultraviolet radiation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676401A (en) * 1964-11-16 1972-07-11 Eastman Kodak Co Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator
US3860538A (en) * 1972-04-07 1975-01-14 James Edwin Guillet Photodegradable polymer masterbatches
CA1073581A (fr) * 1974-01-25 1980-03-11 Canadian Titanium Pigments Ltd. Matiere aux polyolefines photodegradables
US4495311A (en) * 1972-07-06 1985-01-22 Princeton Polymer Laboratories, Inc. Degradable hydrocarbon polymers

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990006966A1 (fr) * 1988-12-22 1990-06-28 The Dow Chemical Company Agents de photodegradation et de thermocollage pour materiaux de matrices polymeres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676401A (en) * 1964-11-16 1972-07-11 Eastman Kodak Co Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator
US3860538A (en) * 1972-04-07 1975-01-14 James Edwin Guillet Photodegradable polymer masterbatches
US4495311A (en) * 1972-07-06 1985-01-22 Princeton Polymer Laboratories, Inc. Degradable hydrocarbon polymers
CA1073581A (fr) * 1974-01-25 1980-03-11 Canadian Titanium Pigments Ltd. Matiere aux polyolefines photodegradables

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0486524A4 *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2061405A2 (es) * 1993-05-04 1994-12-01 Univ Granada Produccion de polihidroxialcanoatos (phas) por azotobacter chroococcum pha.
EP0669374A3 (fr) * 1994-02-25 1996-02-28 Bp Chem Int Ltd Mélanges de polymères.
US5859129A (en) * 1994-02-25 1999-01-12 Bp Chemicals Limited Polymer blends
EP0909791A3 (fr) * 1994-02-25 2002-03-06 BP Chemicals Limited Compositions de polymères à partir de polycétones
WO1996006889A1 (fr) * 1994-08-26 1996-03-07 Bp Chemicals Limited Melanges de polycetone et de polyethylene basse densite a structure lineaire
US5859138A (en) * 1994-08-26 1999-01-12 Bp Chemicals Limited Polymer blends
WO2000031166A1 (fr) * 1998-11-19 2000-06-02 Uni Chem Co., Ltd. Film plastique bio-photodegradable, composition de charge plastique afferente et procede de preparation de cette composition
US8859671B2 (en) 2009-12-11 2014-10-14 Dow Global Technologies Llc Photodegradable films with good tensile and dart properties
WO2011071843A1 (fr) * 2009-12-11 2011-06-16 Dow Global Technologies Llc Films photodégradables avec bonnes propriétés à la traction et à l'essai de résistance au choc au mouton
CN102753615A (zh) * 2009-12-11 2012-10-24 陶氏环球技术有限责任公司 具有良好的拉伸和落镖性质的光可降解的膜
US20120289645A1 (en) * 2009-12-11 2012-11-15 Tice Colleen M Photodegradable Films with Good Tensile and Dart Properties
WO2014105608A1 (fr) 2012-12-28 2014-07-03 Dow Global Technologies Llc Polymères à base d'éthylène et leurs procédés de production
US9523015B2 (en) 2012-12-28 2016-12-20 Dow Global Technologies Llc Ethylene-based polymers and processes to make the same
EP3470483A1 (fr) 2012-12-28 2019-04-17 Dow Global Technologies Llc Polymères à base d'éthylène et leurs procédés de production
WO2015200426A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Polymères à base d'éthylène comprenant des motifs dérivés du monoxyde de carbone et d'un agent modifiant la rhéologie
WO2015200430A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Procédé pour préparer des polymères à base d'éthylène à l'aide d'une distribution de monoxyde de carbone
US9856338B2 (en) 2014-06-27 2018-01-02 Dow Global Technologies Llc Processes to prepare ethylene-based polymers using a distribution of carbon monoxide
US10654955B2 (en) 2014-06-27 2020-05-19 Dow Global Technologies Llc Ethylene-based polymers comprising units derived from carbon monoxide and a rheology modifying agent
WO2017189299A1 (fr) 2016-04-29 2017-11-02 Dow Global Technologies Llc Compositions comprenant des copolymères d'éthylène-monoxyde de carbone
US10815375B2 (en) 2016-04-29 2020-10-27 Dow Global Technologies Llc Compositions comprising ethylene-carbon monoxide copolymers
WO2019089750A1 (fr) 2017-10-31 2019-05-09 Dow Global Technologies Llc Interpolymères d'éthylène/co et procédés de fabrication associés
US11542368B2 (en) 2017-10-31 2023-01-03 Dow Global Technologies Llc Ethylene/CO interpolymers and processes to make the same

Also Published As

Publication number Publication date
EP0486524A4 (en) 1992-12-09
EP0486524A1 (fr) 1992-05-27
JPH04504734A (ja) 1992-08-20
AU6148190A (en) 1991-12-31

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