WO1990011329A1 - Compositions thermoplastiques calendrables contenant des polyurethanes lineaires laminables - Google Patents

Compositions thermoplastiques calendrables contenant des polyurethanes lineaires laminables Download PDF

Info

Publication number
WO1990011329A1
WO1990011329A1 PCT/US1990/001475 US9001475W WO9011329A1 WO 1990011329 A1 WO1990011329 A1 WO 1990011329A1 US 9001475 W US9001475 W US 9001475W WO 9011329 A1 WO9011329 A1 WO 9011329A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
thermoplastic
polyurethane
amount
present
Prior art date
Application number
PCT/US1990/001475
Other languages
English (en)
Inventor
John R. Damewood
Jill R. Menzel
Fred N. Teumac
Bert A. Ross
Original Assignee
Reeves Brothers, Inc.
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
Priority claimed from US07/326,182 external-priority patent/US5248731A/en
Priority claimed from US07/326,818 external-priority patent/US5130384A/en
Application filed by Reeves Brothers, Inc. filed Critical Reeves Brothers, Inc.
Publication of WO1990011329A1 publication Critical patent/WO1990011329A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • This invention relates to a method for lowering the processing temperature of hard to process thermoplastic materials so that they can be calendered on conventional rubber processing equipment.
  • This invention can also be used for improving the processability of certain thermoplastic materials which are extruded or injection molded.
  • Blends of thermoplastic materials such as polyurethanes and polyvinyl chloride, nitrile rubber and polyvinyl chloride, and many other polymeric materials are well known and have been used for a variety of applications. Such blends are useful for applications such as coated fabrics, molded products, etc. ; however many of these materials have relatively high processing temperatures and ar difficult to handle for this reason. Specialized equipment i required for manufacturing these materials into a final product. If the processing temperatures of these thermoplastic materials could be reduced without sacrificing the performance of such materials, it would be possible for the manufacturer to obtain substantial savings in energy costs, or, for the same expenditure of energy, to obtain end products of higher quality more easily or more rapidly.
  • thermoplastic compositio having improved temperature processing characteristics comprising a thermoplastic synthetic polymeric material havin a processing temperature in the range of between about 150 an 325°F; and a millable linear thermoplastic polyurethane elastomer in an amount sufficient to lower the processing temperature of the thermoplastic material by at least about
  • the thermoplastic material is a polyamide, polyolefin, or polyurethane, and is present in an amount of between about 5 and 95 weight percent.
  • the composition may further contain an agent for curing the linear thermoplastic millable polyurethane elastomer to improve the tensile strength properties of the overall composition.
  • a particularly preferred composition has the thermoplastic material present in an amount of between about 70 and 90 weight percent and the polyurethane is present in an amount of between about 10 and 30 weight percent.
  • this polyurethane it is advantageous to have this polyurethane present in an amount sufficient to reduce the processing temperature of the thermoplastic material by at least 15 to 20°F, and this can be achieved by utilizing the preferred ranges.
  • thermoplastic synthetic polymeric material which is normally processable at a temperature between about 150 and 325 ⁇ F which comprises adding thereto a millable thermoplastic linear polyurethane elastomer in an amount sufficient to reduce the processing temperature of the thermoplastic material by at least about 10 ⁇ F, thus forming a thermoplastic composition having reduced temperature processing characteristics.
  • thermoplastic synthetic polymeric material when present in an amount of less than about 50% by weight, the thermoplastic composition may be cured to improve its overall properties.
  • a further embodiment of the invention relates to th thermoplastic composition produced by the inventive method.
  • These compositions are advantageously utilized in a coated fabric article.
  • Such articles are generally in the form of a elongated sheet and the reinforcing material is preferably a fiber of nylon, polyester, cotton, fiberglass or combinations thereof, in either a woven or knit structure.
  • FIG. 1 is a graphical illustration of the difference in processing temperatures for various mixtures of a polyester polyurethane and linear thermoplastic millable polyurethane elastomer in accordance with a preferred embodiment of the invention as set forth in Example 11.
  • the present invention provides one method for improving the processability of many thermoplastic materials by reducing their processing temperatures such that the thermoplastic material is readily processable on conventional rubber processing equipment.
  • This result is achieved by adding a millable thermoplastic linear polyurethane elastomer to the thermoplastic material to form a blend.
  • These blends range from approximately 5 to 95 parts of the polyurethane an 5 to 95 parts of the thermoplastic material.
  • these blends can be processed on conventional rubber equipment ranging from cold to hot mill temperatures.
  • the linear thermoplastic millable polyurethane elastomer to be used in the process of the present invention includes any of the millable polyurethanes known in the art.
  • Typical millable polyurethanes include: Vibrathane V-5008 (Uniroyal Chemical), Millathane HT (TSE Ind.), Morthane CA-1217 (Morton-Thiokol) , and Adiprene E (Uniroyal Chemical) .
  • the most preferred millable polyurethane is Morthane CA-1217; a linear polyurethane made by the reaction of a polyester and 4,4'-diphenylmethane diisocyanate.
  • the amount of linear thermoplastic millable polyurethane elastomer in the blend can range between approximately 5 and 95 parts by weight per 100 parts by weight of the total blend, with the most preferred amounts ranging from 10 to 30 parts by weight of the total blend.
  • amounts of greater than 50 parts of the blend is the millable polyurethane, the blend acts more like the millable polyurethane than the thermoplastic material.
  • a cure package to cure the linear millable polyurethane and improve the physical properties of the blend.
  • Such cure packages generally include sulfur compounds, and are well known by those skilled in the art of vulcanizing rubber. Particularly useful cure packages are set forth in the examples.
  • thermoplastic material we mean a polyurethane, polyolefin, or other thermoplastic polymer which have a processing temperature of between about 150 and 325 ⁇ F.
  • thermoplastic materials covered by this invention include polyamides such as Elvamide 8062 (E.I. duPont), chlorinated polyolefins such as Alcryn (E.I. duPont) and a wide range of thermoplastic polyurethanes, including those based on polyethers, polyesters, polycarbonates or mixtures thereof. All these materials are non-reactive heat processable materials.
  • Specific thermoplastic polyurethanes include the Estanes (B.F. Goodrich), Q-Thanes (K.J. Quinn) an Morthanes (Morton-Thiokol) .
  • Estane 5740 and 5788 are polycarbonate polyurethanes; Q-Thane PS-62 and Estane 58271 are typical polyester polyurethanes; and Q-Thane PE-88 is a typical polyether polyurethane. Blends of these polyurethane are also suitable in the invention.
  • Morthane CA-1225 is a polyurethane formed by the reaction of an aliphatic polycarbonate and polytetramethylene glycol with an aromatic diisocyanate which is suitable for use in this invention. With respect to low temperature impact resistance this material is preferred.
  • thermoplastic materials include linear thermoplastic polyurethane elastomer compositions comprising a mixture of a polycarbonate polyol and a polyether polyol; a diisocyanate compound; and first and second extenders.
  • the diisocyanate compound is initially reacted with one of the extenders in a molar ratio of above 2:1 so as to form a modified diisocyanate component having a functionality of about 2 prior to reaction with the other components.
  • This modified diisocyanate component provides relatively low temperature processing properties to the composition, whereas the polyol mixture provides superior hydrolytic stability and low temperature flexibility to the composition.
  • the first extender component is a polyol or a ine compound having a molecular weight of less than about 500, such as a diol, while the diisocyanate compound primarily comprises 4,4'-diphenyl methane diisocyanate.
  • the first extender component is a polyol or amine compound having a molecular weight between about 60 and 250, such as 1,4-butane diol, tripropylene glycol, dipropylene glycol, propylene glycol, ethylene glycol, 1,6- hexane diol, 1,3-butane diol, neopentyl glycol, ethylene diamine or mixtures thereof.
  • the polyether polyol and polycarbonate polyol are present in a relative amount of between 2:1 to 1:8.
  • the first extender is 1,4-butanediol and the second extender is tripropylene glycol
  • the modified diisocyanate component has an NCO content of between about 14 and 33%, preferably between about 20 and 26%.
  • Any diisocyanate compound is suitable for modification with those based on 4,4 , -diphenyl methane diisocyanate being preferred.
  • Toulene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, xylene diisocyanate and cyclohexane diisocyanate can also be used, if desired, but these compounds are generally more expensive or slower reacting.
  • the relative amount of modified diisocyanate to polyol ranges from above 2:1 to 20:1, and preferably between about 2.5:1 and 8:1.
  • the second extender compound is included in an amount to achieve a final NC0:0H ratio of between about 0.95 to 1.05/1.
  • processing temperature we are referring to th temperature required for converting the polymer into a product.
  • Various processes can be used for achieving this
  • thermoplastic polyester polyurethane can range between about 220 and 280 ⁇ F.
  • millable linear polyurethane such as Morthane
  • the processing temperature can be reduced by between 10 to 30 C F or more. This reduction is achieved because the millable linear polyurethane alone can be processed at a temperature of about 150°F. It was surprising to find that the Morthane CA-1217 is compatible with the thermoplastic 0 materials, since its properties are quite different.
  • thermoplastic material is present in an amount of less than 50 parts, a cure package ca be utilized to crosslink and/or vulcanize the millable linear polyurethane to improve its toughness and the physical
  • the products of the invention have a wide variety o end uses.
  • the millable linear polyurethane modified thermoplastic polyurethanes can be calendered into sheets for manufacture into coated fabrics for air cells or fuel handlin g- applications (i.e., tanks, hose and the like).
  • the calendered sheets of the blend can be reinforced with any of the commonly used fibers including nylon, polyester, cotton, fiberglass or combinations thereof.
  • the thermoplastic polyurethanes in the composition are generally used in a proportion of at least 50% or more, with an 80/20 ratio being most preferred.
  • a mixture of natural or synthetic fibers in mat form may be sufficient, however, it is preferred to use woven or knit blends of the various fibers.
  • woven or knit blends of the various fibers When standard weaving or knitting patterns are used, it is possible to select one type of fiber for use in one direction of the weave or knit, while another type of fiber is used in the opposite direction.
  • Another arrangement utilizes blends of different fibers in each direction. This can be achieved, for example, by alternating strands of the synthetic and natural fibers in the weave or knit. It is also possible to blend the different fibers at the yarn level to form a composite yarn or to intimately blend such materials into a staple fiber. Then, the composite yarn or staple fiber could be used in the form of a mat, woven or knit construction.
  • Such fabric reinforcement generally has a weight of between about 1.5 and 5.5 ounces per square yard, preferably between about 2 and 3 ounces per square yard.
  • the lower processing temperature of the resultant blend enables the blend to possess increased flow properties at the same processing temperature used for the unmodified material; for example, molds can be filled more rapidly in an injection molding process. This would create energy savings by reducing the cycle time for filling the mold. Alternatively, the processing temperatures could be lowered to reduce the amount of energy input into the process.
  • thermoplastic material could be increased, since its combination with the millable linear polyurethane enables the blend to attain a lower processing temperature.
  • thermoplastic elastomer for example, a blen having the characteristics of the millable linear polyurethan
  • This blend would have greater utility for further combination with one of the thermoplastic materials having a processing temperature at the higher end of the claimed rang since there would be less of a possibility of losing the low temperature blend when mixing the components on, for example, a hot roll mill, as would occur if the temperature differential between the millable component and the thermoplastic component is too great.
  • This problem can also be compensated somewhat by pelletizing each component and thoroughly mixing them in a banbury mixer prior to heat processing the blend. Examples
  • MBT is mercaptobenzo thiazole
  • MBTS is mercaptobenz thiazole disulfide
  • Caytur-4 (E.I. duPont) is a mixture of MBT and zinc chloride.
  • Part A is mixed on a rubber mill or in a banbury mixer using procedures which are well known in the art of rubber compounding. If a hot mill i used, a cure package can be added on the mill and the result ⁇ ing polymer mix fed directly to a calender for sheeting out via normal calendering procedures.
  • the preferred method for this composition does not utilize the cure package, and includes pelletizing the banbur stock such that the blend can be extruder fed to calendering or injection molding equipment.
  • the polymer blend prepared i this manner can be processed on a calender at a roll temperature which is about 30°F lower than the processing temperature of the polymer without the millable linear polyurethane.
  • the processing temperature was found to be about 20°F lower than the thermoplastic polyurethane alone.
  • Table IV is a formulation illustrating a blend using 80 parts of a polyester polyurethane (Q-Thane PS-62) with 20 parts of the millable polyurethane Vibrathane V-5008.
  • Vinyzene BP 5-2 (fungicide) 12. .0
  • Titanox 2010 (pigment) 11.4 Yellow Iron Oxide (pigment) 16.8 Black Iron Oxide (pigment) 0.8 Orange Iron Oxide (pigment) 1.0 Levapren 400 12.0 Paraplex G-59 (plasticizer) 30.0 Cure Package (optional)
  • Table V illustrates the compatibility of the millable polyurethane V-5008 with various ratios of the polyester polyurethane Estane 58271.
  • Figure 1 illustrates the difference in processing temperatures for various mixtures of Estane 58271 and Vibrathane V-5008. While the greatest temperature reductions are achieved with the greatest amounts of the Vibrathane material, the tensile strengths of such formulations are also reduced. This reduced strength can be compensated for somewhat by using the cure packages described above in Examples 1 or 10. Above about a 50/50 mixture (wherein the Estane predominates) , a cure package does not provide significant improvements in properties: with greater than about 75% Estane 58271, the cure package actually reduces tensile strength of the mixture and for that reason would not be preferred.

Abstract

Des compositions polymères synthétiques thermoplastiques de certains polyuréthanes, polyamides ou polyoléfines chlorées ayant des températures de traitement dans une plage de 150 à 325°F environ, peuvent être modifiées par addition d'un élastomère de polyuréthane thermoplastique laminable pour abaisser la température de traitement de 10 à 30°F ou davantage. Cette modification permet de traiter la composition thermoplastique sur un équipement de calendrage ou d'extrusion classique en utilisant moins d'énergie ou avec un meilleur rendement. L'invention concerne également des tissus revêtus avec ces compositions thermoplastiques et d'un renforcement à base de fibres.
PCT/US1990/001475 1989-03-20 1990-03-19 Compositions thermoplastiques calendrables contenant des polyurethanes lineaires laminables WO1990011329A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US326,182 1989-03-20
US326,818 1989-03-20
US07/326,182 US5248731A (en) 1989-03-20 1989-03-20 Calenderable thermoplastic compositions containing millable linear polyurethanes
US07/326,818 US5130384A (en) 1989-03-20 1989-03-20 Calenderable thermoplastic polyurethane elastomer compositions containing millable linear polyurethanes

Publications (1)

Publication Number Publication Date
WO1990011329A1 true WO1990011329A1 (fr) 1990-10-04

Family

ID=26985287

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/001475 WO1990011329A1 (fr) 1989-03-20 1990-03-19 Compositions thermoplastiques calendrables contenant des polyurethanes lineaires laminables

Country Status (2)

Country Link
AU (1) AU5346990A (fr)
WO (1) WO1990011329A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5203189A (en) * 1991-11-06 1993-04-20 Minnesota Mining And Manufacturing Company High-intensity roto peen flaps, method of making same, wheels incorporating same, and methods of using wheels incorporating same
US5298303A (en) * 1989-03-20 1994-03-29 Reeves Brothers, Inc. Fabric structure for severe use applications
FR2988394A1 (fr) * 2012-03-26 2013-09-27 Rhodia Operations Agent fluidifiant et procede utilisant cet agent
CN108485240A (zh) * 2018-04-28 2018-09-04 广州顺力聚氨酯科技有限公司 聚氨酯弹性体材料及其制备方法和应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3043807A (en) * 1958-01-27 1962-07-10 Goodyear Tire & Rubber Polyurethane elastomers
US3926826A (en) * 1973-06-18 1975-12-16 Du Pont Magnetic tape binder from a polyurethane, a polyol and an isocyanate
US4261946A (en) * 1978-12-16 1981-04-14 Bayer Aktiengesellschaft Process for the production of thermoplastic polymer by introducing thermoplastic polymer into an extruder and adding organic polyisocyanate and chain lengthening agent
US4419499A (en) * 1982-03-25 1983-12-06 Monsanto Company Compositions of urethane rubber and nylon
US4446286A (en) * 1982-08-02 1984-05-01 The B. F. Goodrich Company Electron beam curable polyrethane compositions
US4483900A (en) * 1982-07-15 1984-11-20 Oakwood Industries, Inc. Polytetrafluorethylene-polyurethane coated fabric
US4560611A (en) * 1981-07-24 1985-12-24 Toray Industries, Incorporated Moisture-permeable waterproof coated fabric
US4619955A (en) * 1984-12-27 1986-10-28 The Sherwin-Williams Company Isocyanate functional urethanes as flexibilizing additives in coating vehicles
US4758465A (en) * 1987-01-02 1988-07-19 Graniteville Company Lightweight tenting fabric
US4889915A (en) * 1987-04-14 1989-12-26 Caschem, Inc. Urethane adhesives

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3043807A (en) * 1958-01-27 1962-07-10 Goodyear Tire & Rubber Polyurethane elastomers
US3926826A (en) * 1973-06-18 1975-12-16 Du Pont Magnetic tape binder from a polyurethane, a polyol and an isocyanate
US4261946A (en) * 1978-12-16 1981-04-14 Bayer Aktiengesellschaft Process for the production of thermoplastic polymer by introducing thermoplastic polymer into an extruder and adding organic polyisocyanate and chain lengthening agent
US4560611A (en) * 1981-07-24 1985-12-24 Toray Industries, Incorporated Moisture-permeable waterproof coated fabric
US4419499A (en) * 1982-03-25 1983-12-06 Monsanto Company Compositions of urethane rubber and nylon
US4483900A (en) * 1982-07-15 1984-11-20 Oakwood Industries, Inc. Polytetrafluorethylene-polyurethane coated fabric
US4446286A (en) * 1982-08-02 1984-05-01 The B. F. Goodrich Company Electron beam curable polyrethane compositions
US4619955A (en) * 1984-12-27 1986-10-28 The Sherwin-Williams Company Isocyanate functional urethanes as flexibilizing additives in coating vehicles
US4758465A (en) * 1987-01-02 1988-07-19 Graniteville Company Lightweight tenting fabric
US4889915A (en) * 1987-04-14 1989-12-26 Caschem, Inc. Urethane adhesives

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298303A (en) * 1989-03-20 1994-03-29 Reeves Brothers, Inc. Fabric structure for severe use applications
US5203189A (en) * 1991-11-06 1993-04-20 Minnesota Mining And Manufacturing Company High-intensity roto peen flaps, method of making same, wheels incorporating same, and methods of using wheels incorporating same
FR2988394A1 (fr) * 2012-03-26 2013-09-27 Rhodia Operations Agent fluidifiant et procede utilisant cet agent
WO2013144034A1 (fr) 2012-03-26 2013-10-03 Rhodia Operations Agent fluidifiant et procede utilisant cet agent
US9290657B2 (en) 2012-03-26 2016-03-22 Rhodia Operations Fluidizing agent and method using said agent
CN108485240A (zh) * 2018-04-28 2018-09-04 广州顺力聚氨酯科技有限公司 聚氨酯弹性体材料及其制备方法和应用
CN108485240B (zh) * 2018-04-28 2021-02-12 广州顺力聚氨酯科技有限公司 聚氨酯弹性体材料及其制备方法和应用

Also Published As

Publication number Publication date
AU5346990A (en) 1990-10-22

Similar Documents

Publication Publication Date Title
EP0131714B1 (fr) Matières plastiques de polyuréthane à résistance au choc
JP5751832B2 (ja) 軟質で弾性の可塑剤非含有熱可塑性ポリウレタンおよびそれを合成するプロセス
US5149739A (en) Fiber-reinforced thermoplastic elastomer polyurethane compositions with either modified and/or unmodified polyolefins
US3882191A (en) Blend of thermoplastic polyurethane elastomer, polyvinyl chloride resin and chlorinated polyethylene
JP2011500926A5 (fr)
ATE342308T1 (de) Reaktive polymer zusammensetzungen mit thermoplastischem polyurethan
US4990557A (en) Mechanically compatible polyurethane/polyolefin thermoplastic polymeric blends
US3984493A (en) Homogeneous blend of vinyl chloride polymer with thermoplastic polyester-urethane
US5932353A (en) Rigid thermoplastic article having soft covering
US3929928A (en) Blend of thermoplastic polyurethane elastomer, chlorinated polyethylene, and additional polyethylene
US6174959B1 (en) Compatible blends of thermoplastic polyurethane with certain polyolefins
EP3289018A1 (fr) Composition polymère comprenant un polyuréthane thermoplastique et une polyoléfine
US5248731A (en) Calenderable thermoplastic compositions containing millable linear polyurethanes
WO1990011329A1 (fr) Compositions thermoplastiques calendrables contenant des polyurethanes lineaires laminables
US5130384A (en) Calenderable thermoplastic polyurethane elastomer compositions containing millable linear polyurethanes
CA2056776A1 (fr) Resines thermoplastiques regenerees de masse moleculaire elevee; procede de regeneration de resines thermoplastiques
JPH061912A (ja) ラバースイッチ用エラストマー複合体
KR102469737B1 (ko) 신발 밑창 용도로 적합한 열가소성 폴리에스테르계 엘라스토머 수지 조성물 및 이를 포함하는 성형품
JP3627409B2 (ja) 熱可塑性エラストマー組成物およびその製造方法
JP3629737B2 (ja) 塩化ビニル系重合体−ポリウレタン複合体の製造方法
JPS621715A (ja) ポリ塩化ビニル−ポリウレタン系複合体の製造方法
JP3513895B2 (ja) 塩化ビニル系重合体−ポリウレタン複合体の製造方法
JP3513896B2 (ja) 塩化ビニル系重合体−ポリウレタン複合体の製造方法
JPH0375574B2 (fr)
CN113278127A (zh) 一种基于聚氨酯改性的弹性材料及其制备方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA FI JP KR NO

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE