JPS63312312A - Active hydrogen composition and formed foam polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the production of polymeric foams, and more particularly to active hydrogen compositions and the production of polymeric foams with high impact strength and good thermal stability. The present invention relates to a molded polyurethane foam characterized by having the following properties.

[Conventional technology and problems]

Molded cellular polymers with polyurethane or polyurethane-polyisocyanurate linkages are well known and have been available on the market for some time.

For example, U.S. Patent No. 3,655,597 states:
Organic polyisocyanate, polyol, non-aqueous blowing agent,
It is disclosed that a molded polyurethane with a dense skin can be obtained by reacting a diamine and a catalyst together. U.S. Patent No. 3,836,424 states:
A molded polyisocyanurate foam article having a skin with improved impact resistance is disclosed.

More recently, molded cellular polymers have been produced by the reaction injection molding (RIM) process. U.S. Patent No. 4,29
No. 2,411 discloses an improved process consisting of the use of a catalyst combination of an organic initiator containing at least one primary or secondary amine and an organic bismuth compound. Initiators include polyoxypropylene diamines with molecular weights up to 1000. Common polyols have at least two hydroxyl groups,
Polyester polyols made from polycarboxylic acids and excess low molecular weight polyols are disclosed.

U.S. Pat. No. 4,263,408 discloses molded cellular foams made from a combination of special catalysts and aliphatic or cycloaliphatic polyisocyanates. These molded products are characterized by good weather resistance and non-yellowing.

Most recently, U.S. Pat. No. 4,530,941 discloses polyurethanes and polyurethane-polyisocyanurate moldings in which some or all of the polyol portions of the components are replaced with relatively high molecular weight aminated polyethers. The manufacture of various molded forms, including products, is disclosed. When produced by the disclosed method with high concentrations of filler, the molded structural foam product has excellent impact strength, but a decrease in thermal stability occurs.

[Means for solving problems]

By using certain polyester polyol mixtures in combination with certain aminated polyethers, molded cellular polyurethanes can be produced that have improved impact strength while exhibiting little, if any, loss in thermal stability. There was found.

The present invention comprises a mixture of the following components: A, (i) an aromatic polycarboxylic acid compound containing two or more carboxylic acid groups, and (ii) having from 2 to 8 hydroxyl groups and an equivalent weight of from 30 to 250. A polyester polyol mixture derived from the reaction of a small amount (in excess of one polyol, and 5 to 30% by weight, based on the total amount of B, (A) and (B)) with a molecular weight greater than 1500 and an amine Novel active hydrogen compositions and processes thereof characterized in that they contain primary or secondary amine-terminated polyethers with a functionality of 2 to 8 and in which more than 50% of the active hydrogens are present in the form of amine hydrogens. .

The present invention is further provided by combining an organic polyisocyanate, a polyol and an extender in the presence of a blowing agent and a urethane-forming catalyst in a mold, said polyol and extender comprising said active hydrogen composition. The present invention relates to a molded cellular polymer and a process thereof.

The invention further relates to said active hydrogen composition additionally comprising 1 to 30% by weight of a fluorocarbon blowing agent.

The improved molded cellular polymers of this invention can be made by combining the following components using any conventional molding technique used in the polyurethane art.

The novelty of the product of the invention lies in the use of the specific active hydrogen composition described above, which composition itself forms part of the invention.

Any known molding technique may be used, including reaction injection molding (R
IM) method is particularly preferred. U.S. Pat. No. 3,655,597, cited above, and U.S. Pat.
No. 836,424, No. 4.292,411, No. 4
, 263,408 and 4,530,941 can be used with the compositions and molded polymers of the present invention.

When active hydrogen compositions are reacted according to the invention with organic polyisocyanates, the resulting cellular foam moldings have high impact strength. Surprisingly, and unlike the prior art, there is no or little loss of resistance to high temperatures as measured at heat deflection temperature by ASTM Test Method D-648.

Furthermore, the active hydrogen composition is a stable homogeneous blend (generally referred to as the "B-side") that retains its uniformity during storage or when dispersed by equipment such as high-pressure heads and auxiliary equipment commonly used in RIM processes. (known as). This uniformity is maintained even in the presence of low molecular weight glycol components.

Furthermore, the stable blend has excellent miscibility with fluorocarbon blowing agents over the full range of proportions required for any desired density. This property allows the moldings of the invention to be produced using a two-component system in which the A-side contains the polyisocyanate component and the B-side contains all the remaining reactants and auxiliaries.

Polyester polyol mixture of active hydrogen composition (A)
is obtained by reacting an excess of at least one of the above polyols (as described below) with an aromatic polycarboxylic acid compound containing two or more carboxylic acid groups under conventional esterification conditions well known in the art. It will be done.

The aromatic polycarboxylic acid compounds used preferably contain 2 to 3 carboxylic acid groups, optionally in the form of the free acid or the corresponding anhydride. The term "aromatic" means an aromatic nucleus containing from 6 to 12 carbon atoms and includes benzene, toluene, xylene, naphthalene, and nuclei containing two Hensen rings, where the aromatic ring further contains one or more halogens. (fluorine, chlorine, bromine and iodine, especially chlorine and bromine) and compounds substituted with one or more inert substituents, such as alkyl groups having from 1 to 4 carbon atoms.

Aromatic polycarboxylic acid compounds include, for example, isophthalic acid,
Terephthalic acid, phthalic acid and its anhydrides, halogen-substituted phthalic acids such as 3- or 4-chloro, bromo- and iodo-phthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid and its anhydrides, 3.4-) Luene dicarboxylic acid and its anhydride, ■, 5-naphthalene dicarboxylic acid, 4゜4'-dicarboxydiphenyl, 4.41-
Dicarboxydiphenyl sulfone, 4,4'-dicarboxybenzophenone, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenylmethane, trimellitic acid and its anhydride, hemimellitic acid and its anhydride, and trimesine acids, but are not limited to these.

A preferred group of polycarboxylic acid compounds consists of (12) phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid and optionally their anhydrides and the halogenated phthalic acids mentioned above. A particularly preferred group consists of phthalic acid (its anhydride), isophthalic acid and terephthalic acid.

The at least one polyol used in the esterification step preferably has a hydroxyl functionality of 2 to 4 and 30
-150 equivalent weight, most preferably 30-100 equivalent weight. Although it is possible to use a single polyol in excess in the esterification step, it is preferred to use two or more low equivalent weight polyols in combination. There is no need to meet any particular functionality or equivalent weight requirements in the selection of polyols to be used (it just needs to meet the functionality and equivalent weight range limitations set forth above).

Typical polyols that can be used include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol,
tripropylene glycol, 1,4-butanediol,
1.6-hexanediol, neopentyl glycol,
Dibromoneopentyl glycol, glycerin, triols prepared from glycerin and ethylene oxide or propylene oxide in a molar ratio of 1 to 10, trimethylolpropane, pentaerythritol, polyethylene oxyglycols, such as Carboisox 200 and 40G
(supplied by Union Carbide) and similar polypropyleneoxyglycols, butanediol, cyclohexanediol, bisphenol A1 methyl glucoside, sorbitol and mannitol.

Preferred polyol groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, glycerin and 1 to 1
Contains triols made from 0 molar ratios of ethylene oxide or propylene oxide.

The term "excess" with respect to at least one polyol means an excess of polyol or mixture thereof over the stoichiometric amount of one mole of polyol for reaction with each carboxylic acid group present in the polycarboxylic acid compound. do. term"
It is readily apparent to those skilled in the art that "carboxylic acid group" means carbonyl functionality, whether present as part of an anhydride or as a free carboxylic acid group. For example, 2
Functional polycarboxylic acid compounds, such as phthalic anhydride or its free acid, require a stoichiometric molar ratio of polyol (regardless of functionality):polycarboxylic acid compound of 2:1, and are trifunctional. For compounds such as trimellitic anhydride, a 3:1 stoichiometric ratio is required. If more than 1 mole of polyol is used for esterification,
It is clear that the sum of all molar amounts of polyols is included in these ratios. Therefore, an excess of polyol can be used to achieve complete esterification, and furthermore,
Excess liquid polyol can be present as a viscosity modifier and bulking agent in the urethane forming reaction.

The exact excess amount is not particularly critical (as long as the polyester polyol mixture has a suitable viscosity, e.g. less than 100,000 cps, preferably less than 50,000 cps at 25°C, and sufficient free polyol to act as an extender). Advantageously, the excess is in the range from 0.2 to 3.0 mol, preferably from 0.4 to 2.0 mol, per mole of polycarboxylic acid compound.

When carrying out the esterification between a polyol and a polycarboxylic acid compound, as described in the prior literature,
Standard esterification conditions and procedures are used. For example, P
O1urethanes Chemistry an
clTechnology,, Part 1, pp. 45-46, 1
962, 5unders and Fr1sch
% John Wiley &5ons; see U.S. Pat. No. 3,459,733 and U.S. Pat. No. 4,540,771.

For example, esterification is carried out in the absence of solvent under a stream of nitrogen for 150 min.
5 at a temperature of ~250°C, preferably 175-225°C
-40 hours, preferably 8-15 hours. The acid number of the product is usually between 0.5 and 2, preferably below 2.

During the reaction period, the water that forms is removed from the top.

It is advantageous to use catalysts which shorten the esterification period. Examples of the catalyst include p-toluenesulfonic acid, magnesium oxide, calcium oxide, antimony oxide, zinc oxide, lead oxide, magnesium acetate, calcium acetate, zinc acetate, lead acetate, various organic amines, sodium methoxide, potassium methoxide, Sodium alkoxytitanate and tetraalkyl titanate. Optionally, preservatives, antioxidants and other suitable auxiliaries can be added to the polyester during or after manufacture.

The polyester polyol mixture produced by the method described above is characterized by having a hydroxyl equivalent value in the range from 85 to 200, preferably from 90 to 150.

Preferably, the polyamine component (B) is a primary amine having a functionality of 2 to 4. Most preferably, the primary amine terminated polyether has a functionality of 2-3 and a molecular weight within the range of 2000-6000. These amine-terminated polyethers are described in U.S. Pat. No. 3,654,370.
They are easily obtained by reductive amination of suitable precursor polyalkyleneoxypolyols as outlined in the US Pat. Generally speaking, any type of polyether polyol may be used, but it is preferred to use those having secondary hydroxyl groups to facilitate the amination step. In certain amination processes, unaminated polyether polyols may remain mixed with the polyamine product. Generally, the polyamine product has 50% of its active hydrogen
% in the form of amine hydrogen, mostly 80%
Has more amine content. That is, polyamines can include mixtures ranging from components containing polyethers having 100% of their functionality as amines to those having an amine content of greater than 50%.

Representative polyamine-terminated polyethers that meet the above conditions include trade names Jeffamine D-2000 (polyoxypropylene diamine, molecular weight = 2000), Je
ffamine ED-2001 (polyoxypropylene-polyoxyethylenediamine, molecule 1 = 2000)
, Jeffamine T-3000 (polyoxypropylene triamine, molecular weight = 3000) and Jeffamine T-3000 (polyoxypropylene triamine, molecular weight = 3000)
mine T-5000 (polyoxypropylene triamine, molecular weight -5000) from Texaco Chemical Company.

Components (A) and (B) are simply blended together using any convenient means for mixing liquid components to form an active hydrogen composition according to the present invention. Generally, component (B) is mixed with (A
) components in a proportion sufficient to produce improved impact strength while retaining heat resistance in the molded polyurethane.

(B) component, based on the total weight of (A) and (B),
It is advantageous to use proportions of up to 30% by weight, preferably 8 to 25% by weight.

In another embodiment, the active hydrogen composition according to the present invention can be used for long-term storage without fluorocarbon separation.
-30% by weight of fluorocarbon blowing agent may be included. The fluorocarbon blowing agent is preferably in the 2 to 10 weight percent range. Fluorocarbon blowing agents are well known to those skilled in the art and are described in detail in the literature cited above. Examples include, but are not limited to, chlorotrifluoromethane, dichlorodifluoromethane, trichlorofluoromethane, methylene chloride, and chloroform. A particularly preferred blowing agent for inclusion in the active hydrogen composition is trichlorofluoromethane.

In carrying out the production of shaped cellular polymers according to the invention, the novel active hydrogen composition described above can be used directly as a premixed "B-side" blend for reaction with the organic polyisocyanate. Alternatively, the components of the blend, namely the polyester polyol mixture and the amine terminated polyether, can be fed to the reaction site as separate streams. Generally, it is preferred to use a single stream for the B-side, which contains, in addition to the polyol component, a blowing agent, a catalyst, and any other auxiliaries described below.

Any organic polyisocyanate conventionally commonly used in the production of molded cellular polyurethanes may be used in the present invention. The organic polyisocyanates disclosed in the above-mentioned documents are included. Typically, known organic aliphatic or aromatic polyisocyanates having difunctionality or higher are used. Preferred include aromatic polyisocyanates.

Examples include, but are not limited to, 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), m- and p-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and mixtures of these two isomers, 4,4'-methylenebis(phenylisocyanate), 2,4'-methylenebis(phenylisocyanate) and these methylenebis(phenylisocyanate) isomers. methylene bis(phenylisocyanate), including mixtures, 3
．． 3'-dimethyl-4,41-diisocyanatodiphenylmethane; liquefied form of methylenebis(phenylisocyanate), especially liquefied form of 4°4'-methylenebis(phenylisocyanate) (containing up to 20% of the 2,4'-isomer) containing admixtures), e.g. having an isocyanate equivalent weight of 130 to 180, e.g.
- Carbodiimide-containing 4,41-methylenebis(phenylisocyanate) prepared by heating methylenebis(phenylisocyanate) to convert a portion of said isocyanate into carbodiimide; and a small amount (0.04 to 0.0% per equivalent of isocyanate I). 2 equivalents) of (
ffi Liquefied form of 4,4'-methylene bis(phenylisocyanate) reacted with molecular weight glycols such as dipropylene glycol, tripropylene glycol and mixtures thereof; having an isocyanate content of 9 to 20% by weight, and isocyanate-terminated prepolymers made from polyols with a functionality of 2 to 3 selected from polyalkyleneoxy polyols with a molecular weight of 1,000 to 10,000, polytetramethylene glycols with a molecular weight of 1,600 to 5,000, and polyester polyols with a molecular weight of 500 to 8,000. [The above polyol and the above methylene bis(phenylisocyanate) are reacted at a ratio of 0.01 to 0.5 equivalent of the above polyol per 1 equivalent of isocyanate]
; blends or mixtures of the above polyisocyanates and especially liquefied methylene bis(phenylisocyanate);
20-85% (preferably 30-60%) by weight of methylene bis(phenylisocyanate) and the remaining 80-15% (70%) by weight of the mixture with each other and the isocyanate-terminated prepolymer described above;
Polymethylene poly(~40%) with higher functionality than 2 (~40%)
Phenyl isocyanate)
(phenylisocyanate) mixtures. 4.
Those with the 4'-methylene bis(phenylisocyanate) isomer and mixtures containing up to 30% of the corresponding 2,4°-isomer are included in polymethylene poly(phenylisocyanate).

Polymethylene poly(phenylisocyanate) is particularly preferred.

The proportions in which the various reactants are used range from 0.90:1 to t, S: Make sure it falls within the range of 1. If said ratio exceeds 1.2:1, the urethane-forming catalyst used has additional activity as an isocyanate trimerization catalyst, or the isocyanate trimerization catalyst is combined with the required urethane catalyst. It is preferable to use Preferably, this ratio is in the range 0.95:1 to 1.15:1.

Any of the urethane catalysts disclosed in the above references can be used in the process of the present invention. Such catalysts include organic and inorganic acid salts and organometallic derivatives of bismuth, tin, lead, antimony and cobalt, as well as phosphines and tertiary organic amines. Preferred such catalysts are stannous octoate, stannous oleate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin mercaptopropionate, dibutyltin cytodecyl mercap triethylamine, triethylenediamine, dibutyltin bis(isooctylthioglycolate);
N, N, N', N'-tetramethylethylenediamine,
N-methylmorpholine, and N,N-dimethylcyclohexylamine and mixtures of any combinations of the foregoing.

Generally, the catalyst or catalyst mixture (if used) will be in the range of 0.01 to 5% by weight, based on the total weight of all components.

The trimerization catalyst used may be any catalyst known to those skilled in the art that catalyzes the reaction of trimerizing organic isocyanate compounds to form isocyanurate groups. For representative catalysts, see Journal ofCellular
Plastics % January/December 1975, page 329; U.S. Pat. No. 3,745.133, No. 3
．． See No. 896,052, No. 3,899,443, No. 3,903,018, No. 3,954,684, and No. 4,101,465.

As mentioned above, fluorocarbon blowing agents can be used as part of the B-side with the zero invention compositions in the proportions described above. In addition, the specific gravity of the molded polymer produced is 0.
．． The fluorocarbons can be added separately to the reaction components in proportions ranging from 4 to 1.2, preferably from 0.7 to 1.0. Other blowing agents may optionally be used with the fluorocarbons, such as carbon dioxide and small amounts of water to form polyurea bonds, and inert gases (eg, nitrogen, argon).

Other optional additives can be used as a separate stream or dissolved in the B-side. Typical of such additional ingredients are cell stabilizers, surfactants, internal mold release agents, flame retardants, colorants, reinforcing agents, glass fibers, organic fibers, and fillers as taught in the literature cited above. It is. Preferred flame retardant additives include those with active hydrogen reactivity (hydroxyl and amino groups), such as phosphorus-containing flame retardants such as dibromoneopentyl glycol, tris(2-chloroethyl) phosphate, tris(2-
chloropropyl) phosphate, tris(2,3-dibromopropyl)phosphate, and tri(1,3-dichloroisopropyl)phosphate.

The molded product according to the invention comprises an aminopolyether component (
B) is characterized by a high impact strength, which increases proportionally to the level. Surprisingly, this increased impact strength is achieved with little or no loss in the heat resistance of the molded product as measured by heat deflection temperature according to ASTM Test Method D648. In contrast, when a prior art impact-modifying polyol is used in place of an aminated polyether, an increase in impact strength would be expected, but unfortunately,
The heat resistance of the molded product is impaired (see Example 1 below).

A further advantage provided by the present invention is that the molded product may be formulated with flame retardants to meet the UL-994 requirements as shown in Example 1 below.
At least a V-1 rating, and in most cases a V-0 rating, can be easily achieved when tested in a vertical burn test.

Furthermore, the molded product is a tough material with a flexural modulus in excess of 200,000 psi.

Due to the combination of the above-mentioned properties, the molded cellular polymers of the present invention are particularly suitable for the manufacture of cabinet housings in the electrical industry, computer hardware, engineering equipment, medical equipment, etc.; ski cores, office furniture, window frames, and the like; It is particularly useful for any housing or cabinet that requires a UL-94V-0 rating with high strength and high resistance to heat that may be generated by the cabinet throat contents.

〔Example〕

The following non-limiting examples illustrate methods of making and using the subject matter of the invention and represent the best embodiments of the invention considered by the inventors.

Flaming This example shows two molded cellular foams according to the invention (Forms A and B) along with control foams (CFI-CF6) molded using the ingredients in the proportions shown in parts by weight in Table 1. ) is shown.

Component A containing polyisocyanate (at 20°C) was added to the first
Similarly, 20'c of component B containing the components shown in the table was added to 1
The foam was made using a bench scale preparation mixed in a quart (approximately 1.10β) cup. The reactants were stirred rapidly for 5 seconds using a stirrer driven at high speed (2400 rpm) and then immediately incubated at 20°C at 65°C.
It was poured into a cm x 20 cm x 6 mm talamcinil shaped aluminum mold. The demold time was 2z minutes without post-curing and the samples were tested for the properties listed in Table 1.

The polyester polyol used was, for example, 920 g (10 mol) of glycerol, 22
30 g (16,64 mol) dipropylene glycol,
Then 1660 g (10 moles) of terephthalic acid and 2.
88 g (0.06% by weight of total ingredients) of esterification catalyst Fascat 4100 (M & T
Chemicals). The mixture was gradually heated and after a total of 9-12 hours the temperature of the solution reached 205°C, at which time the theoretical amount of product water was recovered; equivalent weight -103, viscosity -10000 cps (2
Form A contains 9% by weight of polypropylene oxytriamine with respect to the total amount with the polyester polyol. It is characterized by having excellent impact strength, heat deflection temperature and UL-V-0 rating as shown in the table. In Form B, increasing the polypropylene oxytriamine to 23% by weight further increased the impact strength while retaining a high level of HDT and reduced the fire resistance to a V-1 rating.

For comparison, CFl without polypropylene oxytriamine and with UL-94 and )(DT properties) comparable to Form 8 had significantly inferior impact strength.

Known impact-modifying polyols, such as A-1228
CF2 at a concentration equivalent to the triamine in A and B.
and CF3, respectively, the impact strength was improved, but the HDT value was decreased, especially at a concentration of 23% by weight in CF3. ) This same decrease in HDT values was also observed when considering different impact-modifying polyols in the series CF4-CF6. Impact strength was improved in CF5 and CF6 compared to CF4, but the HDT value was decreased.

(Leaving space below) No. J4 Jr. Note: 1 Polyisocyanate I: 40% by weight methylene bis(
phenylisocyanate), the remainder having a functionality higher than 2.

=133゜2 Polyester polyol I: Hydroxyl equivalent = 10
3; Contains 8% by weight glycerin and 28% by weight dipropylene glycol.

"r-5ooo: Polypropyleneoxytriamine with a molecular weight of 500° supplied by Texaco Chemical Company.

' A-1228: Polypropyleneoxypolyethyleneoxytriol with a molecular weight of 6000, OH equivalent weight -200
0i 14-16% ethylene oxy composition;
Powered by Chemical Company.

5EPD-56: Polypropyleneoxypolyethyleneoxydiol with a molecular weight of 2000; oH equivalent = 1000.
Powered by Liteco Chemical Company.

6DE-601”: solution of 85% by weight of pentabromodiphenyl oxide dissolved in polyphosphoric acid ester; Gr
Supplied by eat Lakes Chemical Co.

? FR-20007 Sucrose-based polyol containing about 30% by weight dibromoneopentyl glycol; OH equivalent -125°8DC-193: Silicone surfactant supplied by Dow Corning.

9 Polycat 32 Tertiary amine catalyst comprising a mixture of dimethylamino-cyclohexylamine and N-methyldicyclohexylamine; supplied by Abbott Laboratories.

Flexural properties measured by I0ASTM test method D-790.

■Charpy impact: Impact resistance test measured according to ASTM test method D-256.

``HDT: Heat deflection temperature measured by ASTM test method D-648.

13UL-94: UL-94-VO is manufactured by Underwriters Labor, North Plutsk, Illinois.
It is the highest rating for non-flammability of plastics when tested in the UL-94 Vertical Burn Test according to the test method described by Atories+Inc. 13cmX]
, 3cm x 1.6n (thickness) test sample. Samples were incubated at 23°C and 50% relative humidity for 48 hours, then at 70°C.
Conditioning is achieved by storage for 168 hours at room temperature and cooling in a desiccator until testing. Hold one end of the sample between clamps and place it in a windless room so that its lower end is 13 cm.
Hang it vertically so that it is suspended above 3Qc+n of the thin cotton layer of J. The 2 cm blue flame of the Bunsen burner is held under the sample for 10 seconds, then removed and the duration of the flame is recorded. Turn on the flame again for 10 seconds. Samples are tested five times for each blend. Observations of the test include the duration of the flame after the first and second flame applications, whether the sample burns up to the clamp, and in particular whether the sample drops a flame drop and ignites the cotton. To achieve UL-94-VO, the sample must not burn for more than 10 seconds after any flame application;
For all 10 applications (5 samples x 2 flame applications each), the total burn time did not exceed 50 seconds, there was no burn to the clamp, no flame drop or cotton ignition occurred, and the second The sample shall not become red hot for longer than 30 seconds after removal of the flame.

(1) This example shows four molded cellular foams C-F according to the invention using the components in the parts by weight proportions shown in Table (1).

Admiral Equipment Company
(a division of the Dow Chemical Company) 2000HP RI
Molded foams were produced using a M machine using two reactant streams. Reactant stream (component) A was polyisocyanate I at 35°C and reactant stream (component) B contained the components listed in Table 1 at a temperature of 38°C. 140 kg of ingredients are mixed using high-pressure impingement mixing head.
Mix with cJ, 25.4 cm x 46 cm x 6
m sealed aluminum molds at 65°C. The demolding time of the molded article was 2z minutes without post-curing.

For foams C, D and E, polyester polyol ■ prepared according to Example 1 above was used, but for foam F
Polyester polyol ■ was used. The latter polyol was prepared in the same way as polyol ①, except that a triol prepared by reacting terephthalic acid, glycerol, dipropylene glycol, and glycerol with propylene oxide in a molar ratio of 1 to 3, respectively, was used as the reactant. Manufactured using. The molar ratio of these components is 1.0: 0.8: 1.73, respectively.
: It was 0.2. The resulting polyol mixture had a hydroxyl equivalent of 106 and a viscosity of 19,000 cps (25°
C) and an acid value of -0.2.

Forms C-F are all HDT as shown in Table ■
It has extremely high impact strength along with excellent heat resistance measured by the value.

(Margin below)

Claims (1)

[Claims] 1. The following components: A, (i) an aromatic polycarboxylic acid compound containing two or more carboxylic acid groups, and (ii) 2 to 8 hydroxyl groups and an equivalent weight of 30 to 250. and 5 to 30% by weight relative to the total amount of B, (A) and (B).
, the molecular weight is greater than 1500 and the amine functionality is 2 to 2.
8, characterized in that it comprises a primary or secondary amine-terminated polyether in which more than 50% of the active hydrogen is present in the form of amine hydrogen. 2. The above polyester polyol mixture (A) is (
derived from the reaction of i) an aromatic polycarboxylic acid compound having 2-3 carboxylic acid groups and (ii) at least one polyol having 2-4 hydroxyl groups and an equivalent weight of 30-150, 2. The composition according to claim 1, wherein ii) is used in an excess of 0.2 to 3 moles per mole of the polycarboxylic acid compound. 3. The polyester polyol mixture (A) is derived from a mixture of terephthalic acid and glycerin and dipropylene glycol, wherein (B) has an amine functionality of 3 and an average molecular weight of 5000. The composition according to item 2. 4. The polyester polyol mixture (A) contains terephthalic acid, glycerin, dipropylene glycol, and glycerin and propylene oxide, respectively.
derived from a mixture of triols prepared by reaction in a molar ratio of 3, wherein (B) has an amine functionality of 3 and 50
3. The composition according to claim 2, which has an average molecular weight of 0.00. 5. The composition of claim 1 further comprising 1 to 30% by weight of a fluorocarbon blowing agent. 6. In a molded cellular polymer obtained by combining an organic polyisocyanate, a polyol and an extender in the presence of a blowing agent and a urethane-forming catalyst in a mold, said polyol and extender are comprised of the following components: A, (i ) an aromatic polycarboxylic acid compound containing 2 or more carboxylic acid groups; and (ii) an excess of at least one polyol having 2 to 8 hydroxyl groups and an equivalent weight of 30 to 250. 5 to 30% by weight based on the total amount of polyester polyol mixture and B, (A) and (B)
, the molecular weight is greater than 1500 and the amine functionality is 2 to 2.
8, characterized in that it has an active hydrogen composition comprising a primary or secondary amine-terminated polyether in which more than 50% of the active hydrogen is present in the form of amine hydrogen. 7. The molding is carried out by a reaction injection molding method;
Polymer according to claim 6. 8. Under reaction injection molding conditions: 1. Polymethylene poly(phenylisocyanate); 2. A. (i) aromatic polycarboxylic acid compound containing 2 to 3 carboxylic acid groups; and (ii) 2 to 3 carboxylic acid groups; the aromatic polycarboxyl compound (i) having 4 hydroxyl groups and an equivalent weight of 30 to 150;
A polyester polyol mixture derived from the reaction of at least one polyol, used in an excess of 0.2 to 3 mol relative to 1 mol, and 5 to 3 mol relative to the total amount of B, (A) and (B). 30% by weight
, molecular weight is 2000-6000 and amine functionality is 2-6000.
3. an active hydrogen composition comprising a primary amine terminated polyether in which more than 50% of the active hydrogen is present in the form of amine hydrogen; 3. a fluorocarbon blowing agent; Equivalent: (A) and (
The ratio of total active hydrogen equivalents of B) is 0.95:1 to 1.15
8. Molded cellular polymer according to claim 7, comprising the reaction product obtained by combining: 9. The molded polymer of claim 8, wherein (B) has an amine functionality of 3 and an average molecular weight of 5000. 10. The polyester polyol mixture (A) is
Derived from terephthalic acid and a mixture of glycerin and dipropylene glycol, or from a mixture of terephthalic acid and a triol prepared by the reaction of glycerin, dipropylene glycol and glycerin with propylene oxide, each in a molar ratio of 1 to 3. 10. A molded polymer according to claim 9, wherein the molded polymer is