WO1991006587A1 - Multicomponent system based on an oxazoline and on a phosphorus-containing compound - Google Patents

Multicomponent system based on an oxazoline and on a phosphorus-containing compound Download PDF

Info

Publication number
WO1991006587A1
WO1991006587A1 PCT/NL1990/000162 NL9000162W WO9106587A1 WO 1991006587 A1 WO1991006587 A1 WO 1991006587A1 NL 9000162 W NL9000162 W NL 9000162W WO 9106587 A1 WO9106587 A1 WO 9106587A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
phosphorus
containing compound
multicomponent system
oxazoline
abo
Prior art date
Application number
PCT/NL1990/000162
Other languages
French (fr)
Inventor
Jacobus Antonius Loontjens
Karel Franciscus Hubertus Bonekamp
Original Assignee
Stamicarbon B.V.
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

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus

Abstract

The invention relates to a multicomponent system based on an oxazoline and a phosphorus-containing compound. The phosphorus-containing compound is a compound according to formula (ABO)PO(OH)2 or (ABO)2PO(OH) or a mixture based on these compounds, A being an acid residue corresponding to acrylic acid, methacrylic acid or crotonic acid and B being corresponding to a branched or non-branched divalent aliphatic alcohol with 2-6 carbon atoms. Preferably, the phosphorus-containing compound is the phosphate ester of hydroxyethylmethacrylate (PEMA). The invention is particularly well-suited for use in reaction injection moulding (RIM) systems.

Description

MULTICOMPONENT SYSTEM BASED ON AN OXAZOLINE AND ON A PHOSPHORUS-CONTAINING COMPOUND

/ BACKGROUND OF THE INVENTION

* The invention relates to a πtulticomponent system

5 based on an oxazoline and on a phosphorus-containing compound.

A multicomponent system based on an oxazoline and on a phosphorus-containing compound is known from US-A-4675371. That patent publication describes the 10 ring-opening polymerization reaction between a compound containing oxazoline groups and an alkenylphosphonic acid. The polymers thus obtained are used, for instance, in reaction injection moulding (RIM) systems.

A disadvantage of said system is that the gelling 15 time of the reaction components in relation to the desired processing speed of the RIM processing equipment is relatively long. In RIM the reaction time generally should be between 5s and 5 min and preferably between 10s and 30s.

20 SUMMARY OF THE INVENTION

The object of the invention is to provide a multicomponent system having such a reactivity of the components that the system can be chooεen such that it is

25 well suited for use in RIM processing equipment.

The multicomponent system according to the invention is characterized in that the phosphorus-containing compound is a compound according to any one of formulas (ABO)PO(OH)2 or (ABO)2PO(OH) or a mixture based on these

30 compounds, A being an acid residue corresponding to acrylic

1 acid, methacrylic acid or crotonic acid and B corresponding to a branched or non-branched divalent aliphatic alcohol with 2-6 carbon atoms. This compound is reacted at suitable conditions of temperature and pressure with an oxazoline at

35 an oxazoline:phosphorus-containing compound ratio of 99:1 to 40:60. The exact structure and composition of the product according to this invention are not known. The product is believed to be a wholly or partially polymerized product containing phosphorus esters and amid groups; however, the structure and composition of the multico ponent product are in no way intended to limit the scope of the invention. According to this invention, systems are obtained having a higher reactivity, which result in the desired gelling time.

Moreover, systems with a higher crosslinking density are obtained.

DETAILED DESCRIPTION OF THE INVENTION

According to a preferred embodiment of the invention, the phosphorus-containing compound is a compound according to formula (ABO)PO(OH)2« The phosphorus-containing compound is preferably a compound in which A is an acid residue derived from methacrylic acid and in which B is derived from an aliphatic alcohol with 2-4 carbon atoms.

Highly suited as phosphorus-containing compound is the phosphate ester of hydroxyethylmethacrylate (PEMA).

The phosphorus-containing compound can be obtained according to the process described in NL-B-161769, or by any other suitable means.

The phosphorus-containing compound, notably the phosphoric acid portion can, but does not necessarily, serve as both a reactant for the RIM system and a catalyst for the oxazoline polymerization.

The oxazoline may be any type of monooxazoline or bisoxazoline, as well as any type of polyoxazoline. Preference is given to the use of a bisoxazoline.

Suitable bisoxazolines include, but are not limited to, 2,2'-bis-2-oxazoline and bisoxazolines in which the chains between the oxazoline groups may be formed by aliphatic groups, cycloaliphatic groups, aromatic groups, polyether groups or polyester groups. The chains are preferably formed by aliphatic groups or by polyether groups because the melting point of the bisoxazoline with such a chain is lower than the melting point of bisozolines with, for example, an aromatic chain. The aliphatic groups have preferably 1-30 carbon atoms, and the polyether groups have preferably 2-30 carbon atoms. A suitable oxazoline is, for instance, 1,4-bis-(2-oxazolinyl-2)butane.

Bisoxazoline can be prepared by any suitable means, for instance, by reacting aminohydroxy compounds with dibasic acids (see Chemical Abstracts, vol. 70, 484531, 1969) or by reacting dinitriles and aminoalcohols (see Liebigs Annalen der Chemie, 1974, pp. 996-1009).

Wholly or partially polymerized reaction products according to the invention are obtained by the copolymerization of the oxazoline with the phosphorus-containing compound at temperatures of between 25°C and 250βC, the molar ratio between oxazoline and the phosphorus-containing compound being between 99:1 and 40:60. Preferably, but not necessarily, the type of polymerization used is cationic ring-opening polymerization, with an additional radical polymerization.

Preferably, the molar ratio of oxazoline and the phosphorous-containing compound is between 95:5 and 45:55, and more preferably this ratio is about 1:1.

Optionally, during the copolymerization, dicarboxylic acids, dithioles, phenols, (esters of) phosphorus-containing acids, maleimideε, isocyanates, compounds containing epoxy groups, lactones and/or anhydrides may, for instance, also be present.

Moreover, in addition to the oxazoline and the phosphorus-containing compound, which participate in the cationic ring-opening polymerization reaction, other compounds, particularly, but not exclusively, those reacting via the radical polymerization mechanism, also may be present during the copolymerization in any desired amount by weight, side by side with, optionally, the previously mentioned compounds. These other compounds are preferably vinyl compounds such as vinyl esters, for instance vinylacetate, styrene, (di) (meth)acrylates, for instance hydroxyethylmethacrylate, (meth)acrylate esters of bisphenol A and/or unsaturated polyesters. Thus, hybrid systems can be formed.

The initiators used for radical polymerization may, for instance, be organic peroxides such as methylethylketone peroxide or dibenzoyl peroxide. The radical polymerization takes place at any suitable temperature and pressure, and usually takes place at a temperature of between 10°C and 200°C at atmospheric pressure.

The multicomponent system is preferably provided as a so-called 'two-can system' or two-component system. Owing to the choice of the various potential reactions in various desired weight ratios, the systems according to the invention are suited for use in a wide variety of applications.

For instance, the system according to the invention (optionally in combination with glass fibers) is highly suited for RIM systems used in the automobile industry and in the electronics industry. For example, in the automotive industry, the present system may be used in the formation of gear-wheels and in the formation of other components that must resist high tension, such as structural parts. In the electronics industry, the present system may be utilized, for example, in the formation of plugs, sockets and printed circuit boards.

Due to the low viscosity of the components of the multicomponent system, the present system is especially suited for application in RIM where fiber reinforcements are placed in the mould before injection of the resin, the so called Structural Reaction Injection Moulding (S-RIM). The system can further be used in RTM (resin transfer moulding) systems.

The system according to the invention, notably a system based on bisoxazoline and PEMA, is further suited also for use as, for instance, crosslinking agent in powder coating formulations, because a reaction with acid-terminated polyesters can take place.

A further area of application is the area of the reactive hot melt adhesives. A reactive hot melt adhesive must be liquid at a certain temperature. Thus, the reaction should start at a certain elevated temperature, and the adhesive must then cure. The adhesion is primarily based on the fact the resin flows into holes and roughnesses on the surface of the material on which the adhesive is applied. The adhesive them stiffens. The present system possesses these characteristics or desirable features. Owing to the presence of phosphorus, there will be good flame-extinguishing properties in the various applications. Thus, the product of this invention would be useful in the aviation, public transport and automotive industries. The invention will be elucidated by means of the following non-restrictive examples.

Examples

Example I

Cationic ring-opening polymerization of 1,4-bis- (2-oxazolinyl-2)-butane under the influence of PEMA

One part by weight l,4-bis-(2-oxazolinyl-2)-butane was placed in a reaction vessel, and the temperature was brought to 165°C. Subsequently, during good stirring, 1 part by weight PEMA was added quickly (so that the oxazoline:PEMA molar ratio was virtually 1:1). A clear solution was formed, which gelled after 28 seconds. The polymer formed was found to be insoluble in hot dimethylformamide. Example II

One part by weight l,4-bis-(2-oxazolinyl-2)-butane and 1 part by weight hydroxyethylmethacrylate (HEMA) were mixed in a reaction vessel, and the temperature in the mixture was brought to 165°C.

Subsequently, during good stirring, 1 part by weight PEMA and 0.1 part by weight methylethylketone peroxide (Butanox M50, Akzo) were added quickly as radical-forming agents. The gelling took place after 9 seconds and the polymer formed did not dissolve in hot dimethyl formamide.

Example III

The experiment was carried out as described in experiment I; yet, a reaction temperature of 100°C was utilized. The solution gelled after 11 s.

Example IV

The experiment was carried out as described in experiment I, with one part by weight of l,4-bis-(2-oxazolinyl-2)-butane. However, half part by weight PEMA was used. A clear solution was formed, which gelled after 9 s. The polymer formed was found to be insoluble in hot dimethylformamide.

Example V The experiment was carried out as described in experiment I, with one part by weight of l,4-bis-(2-oxazolinyl-2)-butane. Yet, 0.1 part by weight PEMA was utilized. A clear solution was formed, which gelled after 3 min. The polymer formed was found to be insoluble in hot dimethylformamide.

Example VI

The experiment was carried out as described in experiment II, however, 0.5 part by weight PEMA was used. The solution gelled after 25 s. The polymer formed was found to be insoluble in hot dimethylformamide.

Example VII

The experiment was carried out as described in experiment II; yet, 0.1 part by weight PEMA was used. The solution gelled after 5.5 min. The polymer formed was insoluble in hot dimethylformamide.

Example VIII

The experiment was carried out as described in experiment II, without HEMA. The solution gelled almost instantaneously. The gelling time was estimated at about 2 s. The polymer formed was found to be insoluble in hot dimethylformamide.

Example IX One part by weight l,4-bis-(2-oxazolinyl-2)-butane and 1 part by weight unsaturated polyester (Synolith 364-A-lR from DSM Resins Holland) were mixed in a reaction vessel, and the temperature was brought to 100°C. Subsequently, during good stirring, 1 part by weight PEMA and 0.1 part by weight methylethylketone peroxide were added quickly. The solution gelled after 22 s. The polymer formed was found to be insoluble in hot dimethylformamide.

Examples I-IX show that the system according to the invention results in short gelling times. For RIM applications a gelling time of 10-30s is preferred, and therefor the oxazoline: phosphorous containing compound ratio preferably is at least about 2:1.

Examples V and VII show a gelling time of 3-5,5 min. This is relatively long for RIM, but is still useable. These gelling times are further well suited for other techniques, such as resin transfer moulding.

Claims

1. Polymerizable multicomponent system comprising oxazoline and a phosphorus-containing compound, wherein: the phosphorus-containing compound has at least one of the formulas (ABO)PO(OH)2 and (ABO)2PO(OH) , wherein: A is an acid residue corresponding to acrylic acid, methacrylic acid or crotonic acid, and
B is corresponding to a branched or non-branched divalent aliphatic alcohol with 2-6 carbon atoms.
2. Multicomponent system according to claim 1, wherein the phosphorus-containing compound is of the formula (ABO)PO(OH)2.
3. Multicomponent system according to claim 1 wherein A is an acid residue corresponding to methacrylic acid and B is corresponding to an aliphatic alcohol with 2-4 carbon atoms. 4. Multicomponent system according to claim 1, wherein the phosphorus-containing compound is the phosphate ester of hydroxyethylmethacrylate. 5. Multicomponent system according to claim 1, wherein the oxazoline is a bisoxazoline. 6. Multicomponent system according to claim 1, wherein the system contains at least one vinyl compound. 7. Multicomponent system according to claim 6, wherein the vinyl compound is at least one of a vinyl ester, styrene, (di) (meth)acrylate and unsaturated polyester. 8. A wholly or partially polymerized reaction product formed from a multicomponent system according to claim
1.
9. The polymerizable multicomponent system of claim 1, wherein said system is polymerized in a reaction injection moulding apparatus.
10. The polymerizable multicomponent system of claim 1, wherein said system is used in the formation of an adhesive. 11. An article of manufacture comprising a polymerized multicomponent system according to claim 1. 12. The article of claim 11 wherein said article is formed by reaction injection moulding.
13. Process for preparing a polymerized reaction product from the multicomponent system of claim 1, comprising reacting the oxazoline and the phosphorus-containing compound at conditions sufficient to induce polymerization.
14. Process according to claim 13, wherein the oxazoline and the phosphorus-containing compound are copolymerized at temperatures of between 50°C and 200°C, and the molar ratio of oxazoline and the phosphorus-containing compound is between 99:1 and 40:60.
15. Process according to claim 13, wherein the phosphorus-containing compound is a compound according to the formula (ABO)PO(OH)2. 16. Process according to claim 13, wherein the phosphorus-containing compound has at least one of the formulas (ABO)PO(OH)2 and (ABO)2PO(OH) wherein: A is an acid residue derived from methacrylic acid and B is derived from an aliphatic alcohol with 2-4 carbon atoms.
17. Process according to claim 13, wherein the phosphorus-containing compound is the phosphate ester of hydroxyester-ethylmethacrylate.
18. Process according to claim 13, wherein the oxazoline is a bisoxazoline.
19. Process according to claim 13, wherein the composition contains at least one vinyl compound.
20. Process according to claim 13, wherein the vinyl compound is at least one of a vinyl ester, styrene, (di) (meth)acrylate and unsaturated polyester.
21. The polymerizable multicomponent system of claim 1 wherein said system is used in the formation of powder coatings. 22. The polymerizable multicomponent system of claim 9, wherein said system is used in structural reaction injection moulding.
PCT/NL1990/000162 1989-10-31 1990-10-30 Multicomponent system based on an oxazoline and on a phosphorus-containing compound WO1991006587A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
NL8902683A NL8902683A (en) 1989-10-31 1989-10-31 Meerkomponentensysteem on the basis of an oxazoline and a phosphorus-containing compound.
NL8902683 1989-10-31

Publications (1)

Publication Number Publication Date
WO1991006587A1 true true WO1991006587A1 (en) 1991-05-16

Family

ID=19855537

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1990/000162 WO1991006587A1 (en) 1989-10-31 1990-10-30 Multicomponent system based on an oxazoline and on a phosphorus-containing compound

Country Status (2)

Country Link
NL (1) NL8902683A (en)
WO (1) WO1991006587A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005085384A1 (en) * 2004-02-17 2005-09-15 National Starch And Chemical Investment Holding Coporation Curable liquid compositions containing bisoxazoline
US7390430B2 (en) 2004-02-17 2008-06-24 National Starch And Chemical Investment Holding Corporation Curable liquid compositions containing bisoxazoline
US7713835B2 (en) * 2006-10-06 2010-05-11 Brewer Science Inc. Thermally decomposable spin-on bonding compositions for temporary wafer bonding
US7935780B2 (en) 2007-06-25 2011-05-03 Brewer Science Inc. High-temperature spin-on temporary bonding compositions
US8092628B2 (en) 2008-10-31 2012-01-10 Brewer Science Inc. Cyclic olefin compositions for temporary wafer bonding
US8771927B2 (en) 2009-04-15 2014-07-08 Brewer Science Inc. Acid-etch resistant, protective coatings
US8852391B2 (en) 2010-06-21 2014-10-07 Brewer Science Inc. Method and apparatus for removing a reversibly mounted device wafer from a carrier substrate
US9099512B2 (en) 2008-01-24 2015-08-04 Brewer Science Inc. Article including a device wafer reversibly mountable to a carrier substrate
US9263314B2 (en) 2010-08-06 2016-02-16 Brewer Science Inc. Multiple bonding layers for thin-wafer handling

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675371A (en) * 1986-05-02 1987-06-23 Ashland Oil, Inc. Thermoset polymeric composition from poly-oxazoline and alkenyl phosphonic acid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675371A (en) * 1986-05-02 1987-06-23 Ashland Oil, Inc. Thermoset polymeric composition from poly-oxazoline and alkenyl phosphonic acid

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005085384A1 (en) * 2004-02-17 2005-09-15 National Starch And Chemical Investment Holding Coporation Curable liquid compositions containing bisoxazoline
US7390430B2 (en) 2004-02-17 2008-06-24 National Starch And Chemical Investment Holding Corporation Curable liquid compositions containing bisoxazoline
US7713835B2 (en) * 2006-10-06 2010-05-11 Brewer Science Inc. Thermally decomposable spin-on bonding compositions for temporary wafer bonding
US7935780B2 (en) 2007-06-25 2011-05-03 Brewer Science Inc. High-temperature spin-on temporary bonding compositions
US8236669B2 (en) 2007-06-25 2012-08-07 Brewer Science Inc. High-temperature spin-on temporary bonding compositions
US9099512B2 (en) 2008-01-24 2015-08-04 Brewer Science Inc. Article including a device wafer reversibly mountable to a carrier substrate
US9111981B2 (en) 2008-01-24 2015-08-18 Brewer Science Inc. Method for reversibly mounting a device wafer to a carrier substrate
US8771442B2 (en) 2008-10-31 2014-07-08 Brewer Science Inc. Cyclic olefin compositions for temporary wafer bonding
US8221571B2 (en) 2008-10-31 2012-07-17 Brewer Science Inc. Cyclic olefin compositions for temporary wafer bonding
US8092628B2 (en) 2008-10-31 2012-01-10 Brewer Science Inc. Cyclic olefin compositions for temporary wafer bonding
US8771927B2 (en) 2009-04-15 2014-07-08 Brewer Science Inc. Acid-etch resistant, protective coatings
US8852391B2 (en) 2010-06-21 2014-10-07 Brewer Science Inc. Method and apparatus for removing a reversibly mounted device wafer from a carrier substrate
US9263314B2 (en) 2010-08-06 2016-02-16 Brewer Science Inc. Multiple bonding layers for thin-wafer handling
US9472436B2 (en) 2010-08-06 2016-10-18 Brewer Science Inc. Multiple bonding layers for thin-wafer handling

Also Published As

Publication number Publication date Type
NL8902683A (en) 1991-05-16 application

Similar Documents

Publication Publication Date Title
US3373221A (en) Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates
US3390121A (en) Color indication in polyester resin curing
US3458460A (en) Unsaturated polyesters cross-linked by diels-alder reaction
US3478126A (en) Urethane modified epoxy ester resin compositions and products
US3420914A (en) Unsaturated polyester compositions and their preparation
US4327013A (en) Poly(acrylate) containing compositions and process for producing molded articles
US5266714A (en) Process for the production of reaction mixtures containing ester polyols
US3466259A (en) Thickened thermosetting vinyl ester resins
US5354821A (en) Radically polymerizable multicomponent mixtures and their use (III)
US4622354A (en) Phase stabilized polyester molding material
US4467071A (en) Epoxy modified structural adhesives having improved heat resistance
US4777195A (en) Curable polyester molding materials
US3935173A (en) Curable compositions
US3362921A (en) Novel elastomeric products obtained from prepolymer compositions
US3278464A (en) Phosphonated polymers
US3282773A (en) Adhesive composition and method of bonding using alpha-cyanoacrylate esters and vinyl aromatics
US4296020A (en) Polyurea thickened molding compositions
US5013631A (en) Ultraviolet curable conformal coatings
US6121398A (en) High modulus polymers and composites from plant oils
US3668139A (en) Catalyst and method of polyester polymerization
US4374229A (en) Thermosetting resinous molding compositions
US3907706A (en) Latent catalyst systems for cationically polymerizable materials
US3506736A (en) Thermosetting resins from polyepoxides,unsaturated polyesters and ethylenically unsaturated carboxylic acids
US5155177A (en) Three component aminoamide acrylate resin compositions
US4477636A (en) Hot-melt adhesive and method

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA FI HU JP KR NO SU US

AL Designated countries for regional patents

Kind code of ref document: A1

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

NENP Non-entry into the national phase in:

Ref country code: CA