JPS5947223A - Highly heat-resistant rigid polyurethane - Google Patents

Abstract

PURPOSE:The titled polyurethane having a high heat distortion temperature and excellent impact resistance, obtained by reacting a specified polyol component with a polyisocyanate component. CONSTITUTION:A highly heat-resistant rigid polyurethane is obtained by reacting a binfunctional, OH-containing polyol component (OH value of 200-700) comprising at least 40wt% 2,2-bis[(2-hydroxypropoxy)phenyl]propane and at most 60wt% 2,2-bis(4-hydroxyphenyl)propane/propylene adduct with an aromatic polyisocyanate (e.g., 2,4-diphenylmethane diisocyanate) at room temperature -120 deg.C and an isocyanate index of 100-180 and heat-treating the product at 140-180 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyurethane, and more particularly to a rigid polyurethane having a high thermal deformability.

Rigid polyurethane is broadly classified into non-foamed molded products and foamed molded products, and foamed molded products are further classified into high-foamed molded products and low-foamed molded products depending on the foaming rate. Non-foamed molded products and low-foamed molded products are used as engineering models for various equipment parts and automobile parts, while highly foamed molded products are mainly used as insulation materials, making them useful resins for an extremely wide range of applications. It is commonly used as.

Conventional rigid polyurethanes contain one or more polyfunctional aliphatic or aromatic polyol monomers, polyoxyalkylene polyols, especially polyoxypropylene polyols, or polyfunctional aliphatic or aromatic polyester polyols. A polyol component consisting of a mixture and a polyisocyanate component consisting of a mixture of one or more aliphatic or aromatic polyisocyanates or polyinthiocyanates are hardened (11) in the presence of a catalyst, a blowing agent, etc. There is.

However, these polyurethane molded products generally have poor heat resistance, and when heat distortion temperature (measured in accordance with ASTM D-64, 8) is taken as a measure for evaluating heat resistance, conventional polyurethane molded products are Sei 80-10
The limit is 0°C, and it was difficult to exceed 100°C with practical strength.

On the other hand, heat resistance can be improved by introducing incyanurate groups obtained by trimerization of isocyanate, but at the same time, the resulting molded product becomes extremely brittle and cannot be put into practical use.

The object of the present invention is to provide a polyurethane having high thermal stability, and in particular, having a high heat distortion temperature of at least 110°C, which could not be achieved with conventional rigid polyurethanes, and having practical strength, especially impact resistance. An object of the present invention is to provide a new rigid polyurethane having properties.

The present invention comprises one or more polyol components having at least difunctional hydroxyl groups and at least one difunctional polyol component.
2,2-bis(2,2-bis(4-(2-hydroxypropoxy)phenyl)propane is a polyurethane obtained by the reaction of one or more polyisocyanate components, the polyol component being 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane as one component. The present invention relates to a rigid polyurethane characterized by using a propylene oxide adduct of 4-hydroxyphenyl)propane.

The hard polyurethane of the present invention can be used in various fields, and is particularly useful as various industrial parts that require heat resistance, such as sliding material parts and corrugated coverings thereof.

In the present invention, as a polyol component, 2,2-bis(4-(2-hydroxypropoxy)phenyl)furopane having the following structure as one component (hereinafter referred to as bisphenol A) is used. A propylene oxide (hereinafter referred to as PO) adduct of PO was used.

As a result, we succeeded in obtaining a hard polyurethane with excellent heat resistance.

Polyurethane obtained by reacting with isocyanate has a high concentration of aromatic rings in the molecular chain and has a rigid molecular structure, so it has a high glass transition point. Therefore, it has excellent thermal stability and exhibits the characteristic of being high even at a heat distortion temperature of C or lower (denoted as HDT).

The bisphenol A-PO adduct of the present invention can be obtained by reacting 1 mole of bisphenol A with 2 moles or more of PO using a known method. That is, the above-mentioned adduct contains as one component 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane in which 1 mol of PO is added to each phenolic hydroxyl group per 1 mol of bisphenol A; The amount is usually about 40% by weight or more, preferably about 80% by weight or more.

Other components include P per mole of bisphenol A.
The adduct containing 3 moles or more of O can be contained in an amount usually not more than about 60% by weight, preferably not more than about 20% by weight. In addition, as another component, an adduct of 2 or 3 moles or more of bisphenol A and PO, which has one or two primary terminal hydroxyl groups, is produced as a by-product during the addition reaction and can be added to the polyol component in any proportion. can be included in

However, the amount of unreacted phenolic hydroxyl groups, such as bisphenol A and POI molar adducts of bisphenol A, must be less than 1% by weight.

If the adduct containing 2 moles of PO to 1 mole of bisphenol A is less than 40% by weight, the concentration of the skeleton of bisphenol A as a polyol component decreases, resulting in a decrease in the heat resistance of the resulting polyurethane.

As the polyisocyanate component of the present invention, various at least difunctional aliphatic, alicyclic, and aromatic polyisocyanates known in the field of polyurethane production can be used, but aromatic polyisocyanates are particularly preferably used. . For example, 4,4-diphenylmethane diisocyanate (MDI) and carposiimide-modified MDI (e.g. Nippon Polyurethane Co., Ltd. MTL), polymethylene polyphenylisocyanate (PAP I), polymeric polyisocyanate (e.g. Bayer Urethane 44)
v), 2,4- and 2,6-) lylene diisocyanate (TDI), ortho-toluidine diisocyanate (T
OD I ), naphthylene diisocyanate (HDT)
, xylylene diisocyanate (XDI), etc. are preferably used.

In the present invention, extremely high HD
Although it is possible to obtain an excellent hard urethane having T,
Furthermore, as a polyol component, the polyol has a difunctional hydroxyl value of at least 200 to 700, preferably 300.
~500 aromatic amine base polyoxyalkylene polyol is used in combination to reduce the average hydroxyl value of the polyol component to 20.
0 to 700, preferably 300 to 500, the impact strength of the polyurethane obtained was surprisingly contrary to expectations, and it was found that a synergistic effect of increasing the impact strength without almost reducing the high HDT was obtained. Ta. That is, the impact strength of the polyurethane using the above two types of polyol components in combination is superior to the impact strength of each polyurethane when the above two types of polyol components are used alone. The reason for this has not yet been fully elucidated, but
Considering that in conventional hard polyurethanes, it is extremely difficult to reduce the impact strength by increasing the HDT, the above-mentioned effects of the present invention are surprising. Furthermore, in the present invention, it has been found that by using the PO adduct of bisphenol A in combination with an aromatic amine-based polyol, not only high HDT and impact strength can be obtained, but also processability, moldability, etc. can be effectively improved. . The improvement in processability referred to here refers to the reduction in the viscosity of the polyol liquid due to the introduction of the aromatic amine-based polyol, and the improvement in so-called compatibility in which the polyol liquid and the polyisocyanate liquid mix well even at room temperature. Further, since the chemical reaction proceeds due to the moderate autocatalytic action of the aromatic tertiary amine, no catalyst is intentionally required. Therefore, there is no need to add a catalyst to the polyol liquid.
One example is that the polyol liquid has excellent storage stability. In addition, improvement in moldability includes the introduction of a primary network using at least a bifunctional aromatic amine-based polyol.

The above-mentioned at least difunctional aromatic amine-based polyoxyalkylene polyol having a hydroxyl value of 200 to 70, preferably 300 to 500, can be prepared by a known method to prepare aromatic monoamines such as aniline or 2.4- and 2.6- 1-lylenediamine (TDA) and so-called crude TDA, 4,4
- polymethylene polyphenylene polyamine, ortho- or meta- or para-phenylene diamine obtained by condensation of diaminodiphenylmethane and aniline with formalin;
It is obtained by adding one or more alkylene oxides such as propylene oxide and ethylene oxide to one or more aromatic diamines and aromatic polyamines such as meta- or para-xylylene diamine, and the free one It is a polyol in which substantially no primary or secondary amine remains. When this polyol is used in combination with a bisphenol A-POO-added polyol, it is particularly preferable that the average hydroxyl value of the polyol component is 300 to 500. Further, the tertiary amine concentration of the polyol used in combination is preferably 3 meq/9 or less, particularly preferably in the range of 0.2 to 1.5 meq/y. Within these ranges, the synergistic effect of ``1'' due to combined use is particularly remarkable.

In addition to the aromatic amines, the following aliphatic glycols and the like can be used as co-initiators in the above-mentioned aromatic amine-based polyols in order to lower the viscosity and improve processability in the synthesis stage. and evaporated ethylene glycol,
Polyfunctional aliphatic glycols such as diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, and sucrose.

Examples include aliphatic amines and aliphatic alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and ethylenediamine. is preferred.

The present invention is characterized in that the polyurethane obtained by reaction with polyisocyanate has a high HDT using a gold polyol component with PO addition of bisphenol A, or a PO adduct of bisphenol A and an aromatic amine-based polyol as a polyol component. In addition, it has excellent workability,
Although these polyol components have moldability, other at least difunctional polyols having a hydroxyl value of 50 to 1830 can be used together in an amount not exceeding 50% by weight based on the total polyol component. It has the effect of improving processability and moldability such as reducing viscosity.

Specific examples of polyols with a hydroxyl value of 50 to 1,830 that are both bifunctional include the following polyols.

(al) An aromatic polyol having a hydroxyl value of 50 to 850 and having at least two functional hydroxyl groups.

(a) A compound obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to a monocyclic or polycyclic aromatic compound having at least two hydroxyl groups such as hydroquinone or pyrogallol-4,4-y12-sopropylidene diphenol. (b) A polyol with a hydroxyl value of 300 to 600 obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to an aromatic polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid. 500 polyols i/X) metaxylylene glycol, paraxylylene glycol)) aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid or their anhydrides or their lower alcohol esters, and/or adipic acid, succinic acid The acid component is aliphatic dicarboxylic acid such as acid, aliphatic polyol such as ethylene glycol, L4-butylene gellicol-trimethylolpropane, I,4-cyclohexanediol, ■,4-cyclohexanedimethanol, β, β, β, β-tetramethyl-2.4,8.10
-tetraoxaspiro(5,5)-undecane-3,9
- Alicyclic polyol such as jetanol or -1- (
(a) Polyester polyester polyester with a hydroxyl value of 50 to 450 containing polyols of (1) and (2) as polyol components.When these aromatic polyols of (a) are used together, the amount should not exceed 50% by weight based on the total polyol, Moreover, it is preferable that the average hydroxyl value is 200 to 500.

(l) Polyfunctional aliphatic glycol having a hydroxyl value of 800 to 1,830.

For example, ethylene glycol, diethylene glycol, propylene gellicol, dipropylene glycol, glycerin, triethanolamine, etc. can be used in combination in an amount of 10% by weight or less based on the total polyol.

(c) A polyfunctional aliphatic polyol having a hydroxyl value of 300 to 800.

Examples: One or more of evasucrose, sorbitol, glucose, penquerythritol, trimethylolpropane, glycerin, ethylenediamine, jetanolamine, water, and one or more alkylene oxides such as propylene oxide and ethylene oxide. "- added polyol, 50% by weight based on the total polyol
It is preferable to use them together within the following ranges.

- The listed polyols are particularly preferred;
830 polyol can be used in combination in an amount not exceeding 50% by weight based on the total polyol.

These polyols must have a moisture content of 0.05% or less, preferably 15-0.02% or less, prior to the reaction with Incyane-1. Also, the polyisocyanates should be sufficiently degassed in advance.

If these are neglected, unnecessary foaming will occur during the curing reaction. However, this is of course not the case when obtaining a foam (r').

The polyol component and the polyisocyanate 1 component can be reacted by a one-shot method or a prepolymer method. The reaction between polyol and polyisocyanate is suitably carried out within the range of isocyanate index of 100 to 180, preferably 105 to 160; outside this range, heat resistance will decrease regardless of whether the isocyanate index becomes small or large. come. Although the cause of this is not clear, it is presumed that it is due to a decrease in the substantial molecular weight of the polymer.

Although the catalyst is not particularly required in the present invention, known catalysts such as tertiary amines such as triethylene diamine and organometallic compounds such as dibutyltin dilaure-1 can also be used. However, the isocyanate 343 catalyst that forms isocyanurate rings is not preferred. It is also possible to prepare a rigid polyurethane containing an inorganic filler by pre-mixing the inorganic filler with the polyol or polyisocyanate. As agents, glass fibers such as milled glass fibers and chopped strand glass fibers,
Examples include graphite, 1.k silicon oxide, aluminum oxide, molybdenum disulfide, etc., and are effective in improving hardness, molding shrinkage rate, coefficient of friction, surface 4-friability, etc. In the present invention, it is also possible to form a foam by using water, a halogenated hydrocarbon such as trifluorotrichloroethane, or an organic blowing agent such as azobisisobutyronitrile.

In the present invention, the curing reaction can be carried out, for example, as follows. First, the liquid temperature of the compound is set to room temperature to 120°C, and the temperature of the casting mold is set to 50 to 120°C, and the mold is cast, hardened, and demolded. Although it has a higher HD T than the molded product, properties such as impact strength can be improved by further heat treating it at a temperature of 140 to 180°C.The heat treatment is performed using air or an inert gas such as nitrogen. It can be done in an atmosphere.

The present invention will be explained below with reference to Examples.

Example 1 Propylene oxide adduct of bisphenol A [manufactured by Toho Chiba Chemical Co., Ltd., rBisol-2PJ (approx. 93% of 2 molar adduct of PO by gas chromatographic analysis, PO
Contains about 7% of the 3 molar adduct of OH value 316] to 100
The mixture was heated to 0.degree. C. and dehydrated under reduced pressure to bring the moisture content to 0.015%. This polyol 100'! (0,563 equivalents) to 5
4 in a beaker with pure MDI (Nippon Polyurethane Co., Ltd.) 747 (0,592 equivalents) which had been brought to 0°C, melted and brought to 50°C.
Propeller type stirring for 0 seconds)! The mixture was stirred in a vacuum desiccator for 1 minute, and then defoamed in a vacuum desiccator for 1 minute. Immediately pour this mixture into
Inner dimensions heated to 0°C: 130 mm x 130 mm x 6 m
The cured product was poured into an assembled glass mold (100 °C) and reacted for 30 minutes in an air bath at 100°C, and then the cured product was taken out from the mold. No bubbles were observed during this time. Next, heat treatment was performed for 2 hours in an air constant temperature bath at 160°C to obtain a non-foamed, tough, rigid polyurethane.

Example 2 TDA-based polyol 50 with an OH number of 400 obtained by addition reaction of 56 moles of propylene oxide and 2.6 moles of ethylene oxide to 1 mole of 2.4-tolylene diamine (TDA). i' CO, 357 equivalent @) 19- and the polyol rBisol-2PJ used in Example 1
Mixed polyol 1 consisting of 50g (0,282 equivalents)
00P and Carposiimide modified MDI (Japan Polyurethane Co., Ltd., [Coronate MTLJNCO content ft28.8%
) 11.2 g (0,768 equivalents) was used in the same manner as in Example 1 to obtain a non-foamed, tough, hard urethane.

However, the liquid temperature was 35° C., and the mold used was an iron mold heated to 1.00° C. and having inner dimensions of 130 mm x 130 mm x 5 mm.

Heat deformation temperature (load 186 to 7/m2) 120°C bending modulus 247ooK7/. m2
Izotsu impact value (with notch) 5, OK grade °C
rT1/10m Example 3 The amount of polyisocyanate in Example 2 was changed to 1497 (1,02
2 Tokuma) and increase the Incyanate index to 160.
A non-foamed, tough, rigid polyurethane was obtained in the same manner as in Example 2, except that

Heat distortion temperature (load 18.6KP/C, 112) 1
31°C20- Flexural modulus 25100 Kfcm2
Izotsu impact value (with notch) 4.8KP°c
m/. □Example 4 After drying 800 mesh carborundum (silicon carbide, Hani Chemicals) at 110°C overnight, "Coronet" MTL
Carborundum was mixed at a ratio of 50 g to JlooF, and the mixture was stirred in a flask at 80°C under reduced pressure for 1 hour, and then returned to normal pressure with nitrogen gas to bring the liquid temperature to 32°C. This polyisocyanate containing carborundum solution 150fF and 300fF
Using 100 g of the mixed polyol used in Example 2 of C, the reaction was carried out in the same manner as in Example 2 to obtain a non-foamed rigid polyurethane containing 20% by weight of carborundum and having a specific gravity of 1.35.

Heat distortion temperature (load 18.6 KIi+/cm2)
121°C flexural modulus 85600
Kai/. m2 Izot impact value (with notch) 2,0~°C
In/Cm Example 5 0.04 P of dibutyltin dilaurate and 20 F of monochlorotrifluoromethane (Freon 11) were mixed with 200 g of the mixed polyol used in Example 2, and the liquid temperature was adjusted to 30°C.
And so.

To this, 30°C polymeric polyisocyanate ``Sumidur 44V-20J (Bayer Urethane Co., Ltd.,
208F (NCO content: 31.0%) was added and stirred vigorously for 15 seconds using a high-speed lab mixer, and the required amount was immediately poured into an aluminum mold at 80°C with internal dimensions of 200 mm x 200 mm x 10 mm, and the mixture was covered with a lid and allowed to foam and harden. 3
After 0 minutes, the mold was demolded and then heat treated in an air constant temperature bath at 140° C. for 2 hours to obtain a rigid polyurethane foam having a specific gravity of 0.32.

Heat distortion temperature (load 4.6 KP/cm2) 1
07℃ flexural modulus 3500 to 7/
cm2 bending strength 102Kg//
Cn12 Izot impact value (without notch) 2. O
K? "Cn1/Cm Example 6 A rigid polyurethane foam having a specific gravity of 0.71 was produced in the same manner as in Example 5.

Heat distortion temperature (load 4゜6 K9/cm2) 12
0℃ flexural modulus 12400 to 97
cm2 bending strength is 573! i! /Cm2 Izot impact value (without notch) 4.2”V
°Cm/cm Example 7 Polyol rBisol'-2P41 used in Example 1
00g and 4,4-diaminodiphenylmethane-based polyoxypropylene glycol rMD-480j (
Mitsui Nisso Tsuurethane Co., Ltd., OI (value 487) 50 g and pentaerythritol-based polyoxypropylene glycol rPE-450J (Mitsui Toatsu Chemical Co., Ltd., OH value 453)
) 50 g of polyols mixed together were dehydrated in the same manner as in Example 1. This mixed polyol 1009. (0,
700 equivalents) and Coronae) MTL123g (0,843
equivalent amount) was reacted at a liquid temperature of 35° C. in the same manner as in Example 2 to obtain 23- non-foamed, tough, rigid polyurethane.

Heat distortion temperature (load 18.6 wcm2) 120°
C-curved elastic modulus 26400 K9/cm” Izot impact value (with notch) 4.6 to 9°
Cm/cm Comparative Example 1 Trimethylolpropane-based polyoxypropylene glycol rT-400J (Adeka Corporation).

100 g (0,6,97 equivalents) of OH number 891) and 1049 (0,768 equivalents) of Sumidur 44V-20 were reacted in the same manner as in Example 2 (however, no heat treatment was performed), resulting in no foaming. A hard polyurethane was obtained.

Heat distortion temperature (load 18.6 KNcm2) 76
°C flexural modulus 28800 to 9/
cm” Izot impact value (with notch) 3.O
K9°cm/cm Comparative Example 2 100 g of the T'DA base polyol used in Example 2 and Coronate MTL 1099 were reacted in the same manner as in Example 224- to obtain a non-foamed rigid polyurethane.

Heat distortion temperature (load 18.6 Kft'/cm2)
102℃ flexural modulus 25100K
g/cm2 Izot impact value (with notch)
8.2 to 9°Cm/cm Comparative Example 3 100 g of the TDA-based polyol used in Example 2, 100 g of the polyol used in Comparative Example 1, 0.049 dibutyltin dilaurate, 20 monochlorotrifluoromethane
The polyol component mixed with g and Sumidur 44V-
A rigid polyurethane foam having a specific gravity of 0.50 was obtained by using 2Q as 2207 in the same manner as in Example 5 (but without heat treatment).

Heat distortion temperature (load 4.6 K9/cm2) '8
3°C bending modulus 6000 K9
/cm2 Bending strength 184K
9/cm29/zotsuto impact value (no notch) 2
．． 8KLi!・Cr]1/cm/l>l L)

Claims (1)

[Scope of Claims] (1) A polyurethane obtained by the reaction of one or more polyol components having at least difunctional hydroxyl groups and one or more polyisocyanate components having at least difunctionality; As the polyol component, 2,2-bis(4,-(2-hydroxypropoxy)phenyl)propane was used as one component (!: t) of a propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane. Incyanate index 100
A rigid polyurethane characterized by reacting in the range of 180 to 180. (2) The average hydroxyl value of the polyol component is 200 or more
700, and an aromatic polyisocyanate is used as the polyisocyanate. +31 -. 1- Hydroxy acid damage to the polyol component 20
Aromatic amine base polyoxyalkylene polyol of 0 to 700 is used in combination to reduce the hydroxyl value of the entire polyol component to 2.
00 to 700. Rigid polyurethane according to claim 1. (4) The polyol component has a hydroxyl value of 300 to 800.
The rigid polyurethane according to claim 1, which is used in combination with a polyfunctional aliphatic polyol. +5) A claim in which the content of 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane in the propylene oxide adduct of 2.2-bis(4-hydroxyphenyl)propane is about 40% by weight or more. Range 1
Rigid polyurethane as described in section. (6) The rigid polyurethane according to claim 5, wherein the content is about 80% by weight or more.