Rigid polyurethane compositions with improved properties

Claim 2

a cyclic monoanhydride of an organic dicarboxylic acid selected from the group consisting of aromatic and cyclo-aliphatic dicarboxylic acids having at least eight carbon atoms and from zero to six halo substituents selected from the group consisting of chloro, bromo and iodo radicals, and

Claim 3

a polymerization starter having at least three active hydrogen atoms and being selected from the group consisting of Mannich condensation products derived from the condensation of a. one mole of a phenolic compound, b. one to two moles of formaldehyde and c. 0.5 to two moles of a nitrogen-containing compound selected from the group consisting of lower aliphatic monoalkanolamines and lower aliphatic dialkanolamines, oxyalkylation products of said Mannich condensation products, and admixtures of said Mannich condensation products with alcohols selected from the group consisting of aliphatic polyalcohols having from three to six carbon atoms and from three to six hydroxyl groups and aminoalcohols having from four to 12 carbon atoms and from three to six active hydrogen atoms, said (1), (2), and (3) being coreacted in intimate admixture at a temperature of from about 50* to about 150* C. for a length of time sufficient for the reactants to copolymerize, with the molar ratios of (1) to (3) ranging from 1.5 to 10 and the molar ratios of (2) to (3) ranging from 0.1 to 1.0.

Claim 4

The polyurethane composition of claim 1 in which said cyclic monoanhydride is tetrabromophthalic anhydride and said monoepoxide is selected from the group consisting of ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide.

Claim 5

The polyurethane composition of claim 1 in which said cyclic monoanhydride is tetrachlorophthalic anhydride and said monoepoxide is selected from the group consisting of ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide.

Claim 6

The polyurethane composition of claim 1 in which said cyclic monoanhydride is 1,4,5,6,7,7-hexachlorobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid anhydride and said monoepoxide is selected from the group consisting of ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide.

Claim 7

The polyurethane composition of claim 1 in which said cyclic monoanhydride is 5,6,7,8,9,9-hexachloro-octahydro-5,8-methano-2, 3-naphthalene dicarboxylic acid anhydride, and said monoepoxide is selected from the group consisting of ethylene oxide and propylene oxide.

Claim 8

The polyurethane composition of claim 1, in which said polyol component contains from 0.01 to 0.5 gram atoms per kilogram of a tertiary aliphatic nitrogen atom in addition to said Mannich nitrogen atoms.

Claim 9

The polyurethane composition of claim 7, with the said polyol component having a RING content of from 0.4 to 1.0 per kilogram.

Claim 10

A flame-retardant polyurethane composition which comprises the reaction product of (A) an organic polyisocyanate having at least two isocyanato groups with (B) a polyol component with an average hydroxyl functionality of from two to ten and an average equivalent weight ranging from about 90 to 250, said polyol component comprising a physical admixture of x. a RING-containing polyol constituent having a number-average molecular weight of from at least 300 to not more than 1,250, a hydroxyl functionality of from at least two to about seven, said RING radicals being selected from the group consisting of aromatic, heterocYclic, and partially or fully saturated cycloaliphatic cyclic hydrocarbon radicals having at least six carbon atoms and from zero to six halo substituents selected from the group consisting of chloro, bromo, and iodo radicals, and said constituent being present in an amount such as to give from 0.5 to 3.0 gram mols of said RING radicals per kilogram of said polyol component, and y. at least ten per cent by weight of said polyol component of a Mannich-condensation-product polyol constituent with a hydroxyl functionality of from three to seven, and equivalent weight of from 90 to 150 and from three to seven hydroxyl radicals per Mannich radical, said Mannich-condensation-product polyol constituent being selected from the group consisting of hydroxyalkylated Mannich condensation products of a phenolic compound, formaldehyde, and a nitrogen-containing compound selected from the group consisting of lower aliphatic monoalkanolamines and lower aliphatic dialkanolamines.

Claim 11

The polyurethane composition of claim 9 in which said polyisocyanate is a polymethylene polyphenylisocyanate.

Claim 12

The polyurethane composition of claim 9 in which said RING-containing polyol constituent is a hydroxyalkylated novolak having an equivalent weight of from about 155 to 190, and an average functionality of from about 2.5 to 5.0.

Claim 13

The polyurethane composition of claim 9 in which said RING-containing polyol constituent is a hydroxyalkylated condensation product of aniline and formaldehyde having an equivalent weight of from about 95 to about 150 and an average functionality of from three to five.

Claim 14

The polyurethane composition of claim 9 in which said RING-containing polyol constituent is a hydroxyalkylated formaldehyde condensation product of a mixture of a phenol and aniline having an equivalent weight of from about 100 to about 200 and an average functionality of from three to six.

Claim 15

The polyurethane composition of claim 9 in which said RING-containing polyol constituent is a hydroxyl-terminated polyester prepared by polycondensation of an acidic compound selected from the group consisting of aromatic and cycloaliphatic carboxylic acids having from three to four carboxylic acid groups and their anhydrides, and alkylene glycols having from two to eight carbon atoms.

Claim 16

The polyurethane composition of claim 9 in which said RING-containing polyol constituent is a polyester prepared by poly-condensation of an aliphatic polyalcohol with a functionality of from three to six, an acidic compound selected from the group consisting of aromatic and cycloaliphatic dicarboxylic acids and their anhydrides, and a difunctional reactant selected from the group consisting of alkylene glycols having from two to eight carbon atoms and aliphatic dicarboxylic acids having from four to 10 carbon atoms.

Claim 17

The polyurethane composition of claim 15 in which said polyol constituent has an equivalent weight of from about 100 to about 250 and said polyol component has a content of from 0.5 to 1.0 RING radicals per kilogram.

Claim 18

The polyurethane composition of claim 15 in which said acidic compound is 1,4,5,6,7,7-hexachlorobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid or its anhydride.

Claim 19

The polyurethane composition of claim 15 in which said acidic compound is tetrabromophthalic anhydride.

Claim 20

The polyurethane composition of claim 15 in which said acidic compound is tetrachlorophthalic anhydride.

Claim 21

The polyurethane composition of claim 15 in which said acidic compound is 5,6,7,8,9,9-hexachloro-5,8-methanooctahydro-2, 3-naphthylene dicarboxylic acid anhydride.

Claim 22

The polyurethane composition of claim 9 in which said RING-containing polyol constituent is a polyester-ether prepared by copolymerization of a lower aliphatic epoxide, a cyclic dicarboxylic acid monoanhydride selected from the group consisting of Aromatic and cycloaliphatic anhydrides having from eight to 14 carbon atoms and zero to six halo substituents selected from the group consisting of chloro, bromo, and iodo radicals and a polymerization starter having at least 3 active hydrogen atoms selected from the group consisting of hydroxyl, carboxyl, and sulfhydryl radicals.

Claim 23

The polyurethane composition of claim 21 in which said RING-containing polyol constituent has a functionality of from about three to six, and said polyol component contains from 0.5 to 1.0 RING radicals per kilogram.

Claim 24

The polyurethane composition of claim 22 in which said epoxide is selected from the group consisting of ethylene oxide, propylene oxide, and 1,2-butylene oxide, and said monoanhydride is 5,6,7,8,9,9-hexachloro-5,8-methanooctahydro-2,3-naphthylene dicarboxylic acid anhydride.

Claim 25

The polyurethane composition of claim 22 in which said epoxide is selected from the group consisting of ethylene oxide, propylene oxide, and 1,2-butylene oxide, and said monoanhydride is 1,4,5,6,7,7-hexachlorobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid anhydride.

Claim 26

The polyurethane composition of claim 22 in which said epoxide is selected from the group consisting of ethylene oxide, propylene oxide, and 1,2-butylene oxide, and said monoanhydride is tetrabromophthalic anhydride.

Claim 27

The polyurethane composition of claim 22 in which said epoxide is selected from the group consisting of ethylene oxide, propylene oxide, and 1,2-butylene oxide, and said monoanhydride is tetrachlorophthalic anhydride.

Claim 28

The polyurethane composition of claim 22 in which said (y) is an alkoxylated condensation product of 1 mole of a phenol with from 0.9 to 1.2 moles of formaldehyde and 0.9 to 1.2 moles of a nitrogen-containing compound selected from the group consisting of lower aliphatic monoalkanolamines and lower aliphatic dialkanolamines.

Claim 29

The polyurethane composition of claim 9, in which said polyol component contains from 0.01 to 0.5 gram atoms per kilogram of a tertiary aliphatic nitrogen atom in addition to said Mannich nitrogen atoms.

Claim 30

The polyurethane composition of 28, with the said polyol component having a RING content of from 0.5 to 1.0 per kilogram.

Claim 31

The polyurethane composition of claim 9 in which the said (x) constituent comprises from 50 to 90 percent by weight of the said polyol component and is selected from the group consisting of oxyalkylation products of novolaks, oxyalkylation products of aniline-formaldehyde condensates, hydroxyl-terminated condensation polyesters derived from aromatic or cycloaliphatic dicarboxylic acids or their anhydrides, and hydroxyl-terminated polyester-ethers derived from aromatic or cycloaliphatic dicarboxylic acids or their anhydrides.

Claim 32

The polyurethane composition of claim 30 in which the said (y) constituent comprises from 10 to 50 percent by weight of the said polyol component.

Claim 33

The polyurethane composition of claim 31 in which the said RING radicals are present in an amount of from 0.5 to 1.0 mols per kilogram of said polyol component, and are residues of a dicarboxylic acid selected from the group consisting of tetrachlorophthalic acid, tetrabromophthalic acid, 1,4,5,6,7,7-hexachlorobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid, and 5, 6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalene dicarboxylic acid.

Claim 34

The polyurethane composition of claim 32 in which the said RING radicals are present in an amount of from 0.5 to 0.8 mols per kilogram of polymer.

Claim 35

The polyurethane composition of claim 9 in which the said RING radical is a residue of the addition product between a halogen and a radical selected from the group consisting of tetrahydro-1,2-phenylene, methyl tetrahydro-1,2-phenylene, and (2,2,1)-bicyclo-2,3-heptenylene-5-.

Claim 36

The polyurethane composition of claim 9 in which the said polyisocyanate is polymethylene polyphenylisocyanate.