Polymerisable plasticiser, liquid polyurethane resin composition comprising same and uses thereof

Abstract

The present invention relates to a polymerisable plasticiser formed by a hydrocarbon chain, one end of which bears more than one isocyanate function, said hydrocarbon chain comprising and/or being substituted by an aromatic ring and/or an aliphatic ring and/or said hydrocarbon chain is substituted by at least two hydrocarbon chains that can comprise an unsaturation, and the number of isocyanate functions being strictly greater than 1, preferably greater than 1.2, and, more preferably, grater than 1.5 but less than or equal to 2.2. The invention also relates to liquid polyurethane resin compositions and, in particular, stable, ready-to-use liquid polyurethane resin compositions comprising said plasticiser. The invention further relates to methods for replacing all or part of the exogenous plasticiser and/or solvent in a polyurethane resin by adding said polymerisable plasticiser.

Claims

1. A polymerizable plasticizer containing a hydrocarbon chain, only one end of which bears more than one isocyanate function, said hydrocarbon chain comprising and/or being substituted with an aromatic ring and/or an aliphatic ring and said hydrocarbon chain being substituted with at least two hydrocarbon chains that comprise an unsaturation, and the number of isocyanate functions being strictly greater than 1 and less than or equal to 2.2.

2. The polymerizable plasticizer according to claim 1, having a viscosity between 400 and 14,000 centipoises.

3. The polymerizable plasticizer according to claim 1, having general formula (I): ##STR00011## wherein each R independently represents a repeating unit which does not comprise any hydroxyl functions or any isocyanate functions and which is chosen from the group consisting of: alkylene, cycloalkylene, arylene, heteroarylene, arylcycloalkylene, arylheterocycloalkylene, heteroarylalkylene, heteroarylcycloalkylene, and monounsaturated or polyunsaturated hydrocarbylene; wherein R′ represents a unit which does not comprise any hydroxyl functions or any isocyanate functions and which is chosen from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, arylcycloalkyl, arylheterocycloalkyl, heteroarylalkyl, heteroarylcycloalkyl, and monounsaturated or polyunsaturated hydrocarbyl; and wherein n is between 2 and 50; and wherein A is a group comprising a number of isocyanate functions strictly greater than 1 and less than or equal to 2.2, on condition that formula (I) comprises either at least one aromatic or aliphatic ring in at least one unit R or at least two alkylene units R substituted with an alkyl chain.

4. A polymerizable plasticizer having general formula (II) ##STR00012## wherein substituents R.sub.1 to 5 are each independently: halogen, alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, arylalkyl, heteroaryl, or monounsaturated or polyunsaturated hydrocarbon chain; and wherein R.sub.1 to 5 do not contain any hydroxyl functions or any isocyanate functions; and wherein at least one from among R.sub.1 to 5 represents a hydrocarbon polymer chain comprising and/or being substituted with at least one repeating unit from the following: alkyl, aryl, arylalkyl, arylcycloalkyl, arylheterocycloalkyl, heteroaryl, heteroarylalkyl, heteroarylcycloalkyl, heteroarylheterocycloalkyl, or hydrocarbyl with at least one unsaturation; and wherein A is a group comprising a number of isocyanate functions strictly greater than 1 and less than or equal to 2.2.

5. The polymerizable plasticizer according to claim 4, wherein the hydrocarbon polymer chain corresponds to general formula (IIIa) or (IIIb): ##STR00013## wherein Z is a carbon and/or oxygen atom; and wherein n is between 2 and 50.

6. The polymerizable plasticizer according to claim 5, wherein the hydrocarbon polymer chain corresponds to general formula (IIIb) wherein n is between 2 and 50 and wherein A is a polymer chain originating from polymeric MDI corresponding to formula (A1): ##STR00014## and wherein A comprises a number of isocyanate functions strictly greater than 1 and less than or equal to 2.2.

7. The polymerizable plasticizer according to claim 5, characterized in that the hydrocarbon polymer chain corresponds to general formula (IIIb), wherein n is between 2 and 50 and wherein A is a radical corresponding to formula (A2): ##STR00015## and wherein A comprises a number of isocyanate functions strictly greater than 1 and less than or equal to 2.2.

8. The polymerizable plasticizer according to claim 4, wherein it is obtained by reaction between: an alcohol compound containing a hydrocarbon chain comprising and/or being substituted with an aromatic ring and/or an aliphatic ring and/or the hydrocarbon chain of the alcohol compound being substituted with at least two hydrocarbon chains that may comprise an unsaturation and wherein the alcohol compound has an —OH number between 0.8% and 2.5% by weight relative to the weight of said compound; and a polyisocyanate comprising 2.1 to 3.2 isocyanate functions.

9. The polymerizable plasticizer according to claim 8, wherein the alcohol compound is a phenolic monoalcohol of general formula (IV): ##STR00016## wherein R.sub.1 to 5 are each independently: halogen, alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, arylalkyl, heteroaryl, or optionally substituted monounsaturated or polyunsaturated hydrocarbon chain; and wherein R.sub.1 to 5 do not contain any hydroxyl functions or any isocyanate functions; and wherein at least one from among R.sub.1 to 5 represents a hydrocarbon polymer chain comprising and/or being substituted with at least one repeating unit from the following: alkyl, aryl, arylalkyl, arylcycloalkyl, arylheterocycloalkyl, heteroaryl, heteroarylalkyl, heteroarylcycloalkyl, heteroarylheterocycloalkyl, or hydrocarbyl with at least one unsaturation.

10. The polymerizable plasticizer according to claim 8, wherein the alcohol compound is a phenolic monoalcohol of general formula (V): ##STR00017## wherein each R represents a unit derived from the polymerization of α-methylstyrene.

11. The polymerizable plasticizer according to claim 8, wherein the alcohol compound is a coumarone resin substituted with a phenol at one end or an a-methylstyrene resin substituted with a phenol at one end.

12. A liquid polyurethane resin composition, comprising at least one polymerizable plasticizer according to claim 1, a prepolymer, and optionally a solvent, a catalyst, liquid fillers and/or solid fillers.

13. A method for reducing the amount of solvent in standard liquid polyurethane resin compositions or bituminous polyurethane resin compositions, comprising the addition of the polymerizable plasticizer according to claim 1 to said polyurethane composition in replacement for some or all of the solvent.

14. A method for reducing the amount of exogenous plasticizer in standard polyurethane resin compositions or bituminous polyurethane resin compositions, comprising the addition of the polymerizable plasticizer according to claim 1 to said polyurethane composition in replacement for some or all of the exogenous plasticizer.

15. The polymerizable plasticizer according to claim 1, wherein it is obtained by reaction between: an alcohol compound containing a hydrocarbon chain comprising and/or being substituted with an aromatic ring and/or an aliphatic ring and the hydrocarbon chain of the alcohol compound being substituted with at least two hydrocarbon chains that comprise an unsaturation and wherein the alcohol compound has an —OH number between 0.8% and 2.5% by weight relative to the weight of said compound; and a polyisocyanate comprising 2.1 to 3.2 isocyanate functions.

16. A liquid polyurethane resin composition, comprising at least one polymerizable plasticizer according to claim 4, a prepolymer, and optionally a solvent, a catalyst, liquid fillers and/or solid fillers.

17. A method for reducing the amount of solvent in standard liquid polyurethane resin compositions or bituminous polyurethane resin compositions, comprising the addition of the polymerizable plasticizer according to claim 4 to said polyurethane composition in replacement for some or all of the solvent.

18. A method for reducing the amount of exogenous plasticizer in standard polyurethane resin compositions or bituminous polyurethane resin compositions, comprising the addition of the polymerizable plasticizer according to claim 4 to said polyurethane composition in replacement for some or all of the exogenous plasticizer.

Description

EXAMPLES

(1) In the examples, the parts are expressed on a weight basis. The viscosities are measured using a Brookfield viscometer, spindle 5 or 6, speed 20 rpm at 23° C., less than one week after manufacturing the product or the composition.

(2) In the examples, the following commercial products and acronyms are used:

(3) Novares® LA 300: phenol-terminated α-methylstyrene resin (CAS 68512-30-1) with an —OH number between 1.7 and 2.2 sold by Rutgers.

(4) Suprasec® 5025: a polymeric MDI containing 2.7 isocyanate functions, sold by Huntsman.

(5) Suprasec® 2385: modified MDI containing 2 isocyanate functions sold by Huntsman.

(6) Desmodur® N3300: HDI trimer containing 3 isocyanate functions sold by Bayer.

(7) Desmodur® L 75: TDI trimer containing 3 isocyanate functions sold by Bayer.

(8) Desmodur® Z 4470: IPDI trimer containing 3 isocyanate functions, dissolved in 70% strength butyl acetate or naptha solvent, sold by Bayer.

(9) Voranol® 2000: polypropylene glycol with a molecular weight of 2,000 g/mol (CAS 025322-69-4) sold by Dow Chemical.

(10) Voranol® CP 450: polypropylene glycol glycerol triol (CAS 025791-96-2) with a molecular weight of 450 g/mol sold by Dow Chemical.

(11) Terathane® 2000: polytetrahydrofuran with a molecular weight of 2,000 g/mol (CAS 24979-97-3) sold by Dupont.

(12) Voranate® T80: TDI sold by Dow Chemical.

(13) Ruetasolv® Di: diisopropylnaphthalene plasticizing aromatic oil sold by Rutgers.

(14) Incozol® LV: bis-oxazolidine comprising a carbonate group (CAS 145899-78-1) sold by Incorez.

(15) PCP 1000: polycaprolactone containing 2 OH functions and having a molecular weight of 1,000 g/mol sold by Solvay.

Example 1

Preparation of a Polymerizable Plasticizer

(16) The following constituents are mixed in a reactor:

(17) 100 parts of Novares® LA 300 resin,

(18) 25 parts of Suprasec® 5025.

(19) The mixture is heated for at least 12 hours at about 100° C.

(20) A polymerizable plasticizer with a viscosity of 1,300 centipoises and a molecular weight of 1,600 g/mol is obtained.

Example 2

Preparation of a Polymerizable Plasticizer

(21) The following constituents are mixed in a reactor:

(22) 100 parts of Novares® LA 300,

(23) 36 parts of Suprasec® 5025.

(24) The mixture is heated for at least 12 hours at about 100° C.

(25) A polymerizable plasticizer with a viscosity of 1,500 centipoises and a molecular weight of 1,300 g/mol is obtained.

Example 3

Preparation of a Polymerizable Plasticizer

(26) The following constituents are mixed in a reactor:

(27) 100 parts of Novares® LA 300,

(28) 36 parts of Desmodura N3300.

(29) The mixture is heated for at least 12 hours at about 100° C.

(30) A polymerizable plasticizer with a viscosity of 9,000 centipoises and a molecular weight of 1,700 g/mol is obtained.

Example 4

Preparation of a Polymerizable Plasticizer

(31) The process is performed as in example 2, the amounts being modified in the following manner:

(32) 100 parts of Novares® LA 300,

(33) 38 parts of Suprasec® 5025.

(34) A polymerizable plasticizer with a viscosity of about 1,500 centipoises and a molecular weight of 2,200 g/mol is obtained.

Example 5

Preparation of a Polymerizable Plasticizer

(35) The process is performed as in example 2, the amounts being modified in the following manner:

(36) 100 parts of Novares® LA 300,

(37) 60 parts of Desmodur® L75.

(38) A polymerizable plasticizer with a viscosity of about 1,200 centipoises and a molecular weight of 1,659 g/mol is obtained.

Example 6

Preparation of a Polymerizable Plasticizer

(39) The process is performed as in example 2, the amounts being modified in the following manner:

(40) 100 parts of Novares® LA 300,

(41) 60 parts of Desmodur® Z 4470.

(42) A polymerizable plasticizer with a viscosity of about 700 centipoises and a molecular weight of 1,666 g/mol is obtained.

Example 7

Preparation of a Polymerizable Plasticizer

(43) The process is performed as in example 2, the amounts being modified in the following manner:

(44) 100 parts of Novares® LA 300,

(45) 40 parts of Desmodur® N 3300.

(46) A polymerizable plasticizer with a viscosity of about 2,500 centipoises and a molecular weight of 1,400 g/mol is obtained.

Example 8

Preparation of a Liquid Polyurethane Resin Composition (Comparative)

(47) The following ingredients are mixed in a reactor so as to form the prepolymer:

(48) 200 parts of Voranol® 2000,

(49) 24 parts of Voranol® CP 450,

(50) 60 parts of Voranate® T80.

(51) The mixture is stirred at 80° C. for 2 hours and, after cooling to about 40° C., the following constituents are added:

(52) 24 parts of xylene,

(53) 150 parts of Ruetasolv® Di,

(54) 200 parts of calcium carbonate as pulverulent filler.

(55) The composition obtained has a Brookfield viscosity (spindle 5, speed 10) at 23° C. of 1,800 centipoises and is applied as an interior coating under tiling. This composition gives off a strong odor of solvent and the coating obtained shows substantial water absorption of about 17% and a lack of adhesion due to the use of plasticizing oil.

Example 9

Preparation of a Liquid Polyurethane Resin Composition Comprising the Polymerizable Plasticizer

(56) The following ingredients are mixed in a reactor so as to form the prepolymer:

(57) 200 parts of Voranol® 2000,

(58) 24 parts of Voranol® CP 450,

(59) 60 parts of Voranate® T80.

(60) The mixture is stirred at 80° C. for 2 hours and the following constituents are then added:

(61) 200 parts of polymerizable plasticizer prepared according to example 4,

(62) 200 parts of pulverulent filler.

(63) A solvent-free liquid one-component composition which has a Brookfield viscosity (spindle 5, speed 10) at 23° C. of 4,500 centipoises is obtained. The composition is applied as an interior coating under tiling. The coating obtained shows water absorption reduced to about 7% and adheres perfectly to the concrete support.

(64) The composition is stored for 4 months at 20° C. After 4 months, the composition rapidly becomes homogeneous when it is mixed with a stick, and no phase separation is observed.

Example 10

Preparation of a Liquid Polyurethane Resin Composition Comprising the Polymerizable Plasticizer

(65) The following ingredients are mixed in a reactor so as to form an MDI masked with hexanol:

(66) 37 parts of Suprasec® 5025,

(67) 10.2 parts of hexanol.

(68) The hexanol is gradually added to the MDI so as to keep the temperature of the reaction mixture below 60° C. When the addition of hexanol is complete, the mixture is left to return to room temperature.

(69) The following ingredients are mixed in a reactor so as to form the prepolymer:

(70) 24 parts of Terathane® 2000,

(71) 6 parts of Suprasec® 2385,

(72) 6 parts of MDI masked with hexanol, synthesized above,

(73) 9 parts of Ruetasolv® Di,

(74) 0.084 part of benzoyl chloride.

(75) The reaction mixture is stirred at 400 rpm for 3 hours at 50° C.

(76) The following ingredients are mixed in a dispersion tank so as to form the polyurethane resin composition:

(77) 48.3 parts of prepolymer synthesized above,

(78) 38.7 parts of polymerizable plasticizer synthesized according to example 1,

(79) 4.3 parts of gray pigment RAL 7040,

(80) 5.9 parts of Incozol® LV,

(81) 2.4 parts of methyltetrahydrophthalic anhydride,

(82) 0.4 part of benzoyl chloride.

(83) The mixture is stirred at room temperature at a speed of 600 rpm for 6 minutes.

(84) A solvent-free liquid one-component composition which has a Brookfield viscosity (spindle 6, speed 20) at 23° C. of 14,000 centipoises is obtained. The composition is applied directly onto concrete as an interior coating under tiling. The coating obtained shows water absorption reduced to about 7% and adheres perfectly to the concrete support.

(85) The composition is stored for 4 months at 20° C. After 4 months, the composition rapidly becomes homogeneous when it is mixed with a stick, and no phase separation is observed.

Example 11

Preparation of a Liquid Polyurethane Resin Composition Comprising the Polymerizable Plasticizer

(86) The following ingredients are mixed in a reactor so as to form the prepolymer:

(87) 540 parts of Voranate® T80,

(88) 90 parts of 1,4-butanediol,

(89) 1000 parts of PCP 1000,

(90) 45 parts of Voranol® CP 450,

(91) 120 parts of butyl acetate.

(92) The mixture is stirred at 80° C. for 1 hour 30 minutes.

(93) The following ingredients are mixed in a dispersion tank so as to form the polyurethane resin composition:

(94) 100 parts of prepolymer synthesized above,

(95) 50 parts of polymerizable plasticizer synthesized according to example 7,

(96) 10 parts of gray pigment RAL 7040,

(97) 14 parts of Incozol® LV,

(98) 1 part of methyltetrahydrophthalic anhydride.

(99) The mixture is stirred at room temperature at a speed of 600 rpm for 6 minutes.

(100) A liquid one-component composition with a low solvent content (4% solvent) which has a Brookfield viscosity (spindle 6, speed 20) at 23° C. of 6,000 centipoises is obtained. The composition is applied directly onto concrete in exterior use, for example on a balcony. The coating obtained shows water absorption reduced to about 7% and adheres perfectly to certain concrete supports.