JPS582314A - Production of polymeric polyol - Google Patents

Abstract

PURPOSE:The polymerization of a specific polyol and an ethylenically unsaturated monomer gives a polymeric polyol having good curing properties with a less amount of a catalyst and giving polyurethane foamed products of high physical and thermal characteristics. CONSTITUTION:The copolymerization is conducted using (A) 100pts.wt. of polyether polyol of 20-50 hydroxyl value and 2-6 functional groups which is prepared by adding an alkylene oxide such as prophylene oxide to a compound with 2 or more active hydrogen atoms such as ethylene glycol and has 8-30wt% of polyoxyethylene chains on the chain terminals and 50-25wt% of random polyoxyalkylene containing oxyethylene groups and oxypropylene groups at a weight ratio of 90/10-30/70 on the inside of molecular chains where the alkylene chains are located on the terminal more than 60% of the total molecular weight and (B) 2-70pts. of an ethylenically unsaturated monomer such as acrylonitrile.

Description

[Detailed description of the invention] The present invention relates to a method for producing polymer polyols.

More specifically, polyurethane is manufactured by the Reaxcon injection molding method (hereinafter abbreviated as RIM method).

) This relates to a method for producing a polymer polyol that provides excellent curing properties and rigidity when used in the production of polyurethane.

In recent years, for example, instrument panels, computer housings,
A need has arisen for urethanes (elastomers, foams, etc.) for automobile steering handles, automobile bumpers, and shock absorbers.

A method for creating urethane molded products applicable to the above uses and the 1M method has been put into practical use. (Refer to Plastics VOL, 2B, 4.1977.)RI
When making urethane molded products for the above-mentioned uses using the M method, the following three requirements are required for the raw material polyol: 1) High reactivity in order to shorten the curing cycle from raw material injection to demolding. 11) Providing a molded product with good initial physical properties to avoid damage when demolding due to a short curing cycle; 111) Providing a molded product with properties that can be used over a wide temperature range (having good temperature characteristics) It is required that the material be a raw material for producing molded products).

However, a raw material that fully satisfies these requirements has not yet been developed. General (To increase reactivity [
A method is adopted in which a large amount of this tertiary amine catalyst is used. death,
However, in this method, when making a molded product, the reaction (foaming) is too fast, the viscosity of the reactant increases quickly, the flowability and workability of the liquid are poor, and the physical properties of the molded product also tend to deteriorate. In addition, since a large amount of expensive amine is used, it has the disadvantage of not being sprayable.

Additionally, cross-linking agents have traditionally been used to give polyurethane rigidity, but using too much cross-linking agents has disadvantages such as poor moldability and initial strength, and it has not been possible to sufficiently increase the rigidity. .

The present inventors have proposed that this J: the above-described RIM without such drawbacks.
As a result of extensive research to find a raw material polyol that satisfies the three requirements specifically required by the law, we found that a specific polymer polyol has the high reactivity that meets the above requirements, and provides polyurethane molded products with high physical properties and good temperature characteristics. They discovered this and arrived at the present invention.

That is, in producing a polymer polyol from a polyol and an ethylenically unsaturated monomer, the present invention provides a polyol having a polyoxyethylene chain at the end of the molecule,
This is a method for producing a polymer polyol characterized by using a polyether polyol having a random polyoxyalkylene chain consisting of a non-terminal (oxyethylene group and an oxypropylene group).

The present invention (polyether polyols conveniently used herein include compounds having at least two active hydrogen atoms (
Examples include compounds having structures in which alkylene oxide is added to polyhydric alcohols, polyhydric phenols, polycarboxylic acids, amines) so as to form the random polyoxyalkylene chains and terminal polyoxyethylene chains, and mixtures thereof. The above polyhydric alcohols include ethylene glycol, propylene glycol, 1.4
-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol dihydric alcohol, glycerin, I-IJ, tyrolpropane, pentaerythritol, sorbitol, methyl glucoside, Polyhydric alcohols with a valence of 8 or more such as sugars; polyhydric phenols such as tehapirocarol, hydroquinone, and other polyhydric phenols, as well as bisphenol A
bisphenols such as; polycarphonic acids include aliphatic polycarboxylic acids such as succinic acid and adipic acid, phthalic acid, terephthalic acid, and trimellitic carboxylic acid 9; and amines include ammonia.

Monoamines (alkylamine, anilino, etc.) x-polyamines (ethylenediamine, diethylene 1-helamine,
(tolylene diamine, piperazine, aminoethylpiperazine, etc.) and alkanolamines (triethanolamine, tripropaturamine, etc.). Two or more kinds of the above-mentioned active hydrogen atom-containing compounds can also be used. Among these, polyhydric alcohols (
Especially ethylene glycol. 14-butanediol, neopentyl glycol, glycerin, trimethylolpropane) and polyhydric phenols (hydroquinone,
hisphenol).

The polyether polyol is prepared by adding a mixture of ethylene oxide and propylene oxide to the above-mentioned compound having at least two active hydrogen atoms (base compound) or its alkylene oxide adduct (base polyether), and then A polyether polyol obtained by adding alkylene oxide if necessary and then adding ethylene oxide to this terminal can be conveniently used.Such a polyether polyol can be represented by the following general formula.

B→(A,0)a-(EO/PO)b-(A,,0
)e-(EO), L-'If)n In the formula, 13 is a residue obtained by removing 11 active hydrogen atoms from a compound having at least 2 active hydrogen atoms; n is an integer of 2 or more, EO/PO is a random polyoxyalkylene group consisting of an oxyethylene group and an oxypropylene group, E
O is an oxyethylene group iA, 0 and A20 are oxyalkylene groups; a, b, c.

(l is 0 or a positive integer, n a, n su,
The n (2, n tl's may be the same or different (the sum of n a's, the sum of ri C's may be 0 or J2).

In the above polyether polyol, the terminal polyoxyethylene chain -(EO) (J- content is at least 8% of the total molecular weight (expressed in weight%). The same applies hereinafter), preferably 10 to 30%, more preferably It is 12-25%.

If the terminal polyoxyethylene chain content is less than 8%, the reactivity is low and it is not possible to form a polyurethane with good curing properties and initial physical properties, and particularly in the case of molding by the RIM method, a satisfactory effect cannot be obtained. Furthermore, if the content of the terminal polyoxine ethylene chain exceeds 30%, the curing properties will improve, but the viscosity will increase and it will become cloudy at a temperature slightly lower than room temperature, resulting in poor workability.In addition, physical properties such as temperature characteristics and water absorption will deteriorate. .

Even if the terminal polyoxyethylene chain content is less than 8%, it can be combined with a terminal polyoxyethylene chain content of 10% or more, or if the terminal polyoxyethylene chain content exceeds 3096, it can be combined with a terminal polyoxyethylene chain content of 30% or less. They can be used in combination so that the (average) terminal polyoxyethylene chain content as a whole falls within the above range.

Also, the ratio (weight ratio) of oxyethylene groups to oxypropylene groups in the random polyoxyalkylene chain -(EO/PO)b- in the polyether polyol chain.
is usually 90:lo to 30:7o, preferably 80:20
~40:60, more preferably 75:25 to 45:5
It is 5. When the proportion of oxyethylene groups exceeds 90, the crystallinity deteriorates, and the resulting polyether polyol becomes cloudy when cold (at a temperature slightly lower than room temperature). Moreover, since the reactivity becomes too high, defects are likely to occur in the surface condition of the molded product.

On the other hand, if the proportion of oxyethylene groups is less than 30%, the internal activation force will be weakened, the curing properties will be reduced, and the initial physical properties of the molded product (D) will be poor.The content of the random polyoxyalkylene chains in the polyether polyol is usually It is at least 5% of the molecular weight, preferably 5 to 25%.If the proportion of random polyoxyalkylene chains is less than 5% of the total molecular weight, only a molded product with low initial strength can be obtained because the internal activation force is small and the curing property is low. If it exceeds 25%, the water absorption of the molded product will be too high and the reactivity will be too high, resulting in the surface condition of the molded product (defects are likely to occur). The proportion is usually 1.5 to 22.5%, preferably 2.0%
~20%.

The position of the random polyoxyalkylene chain (the addition position of the ethylene oxide-propylene oxide mixture) in the polyether polyol is preferably located at the end of 60% of the total molecular weight.

That is, the base polyether (Bf(A,O)a) before lantam addition relative to the molecular weight of the polyether polyol
It is preferable that the molecular weight ratio of T()n) is 60% or more. Propylene oxide is usually used as the alkylene oxide (A, O) used to form the base polyether, but a small amount (for example, 5% or less) of other alkylene oxides (ethylene oxide, butylene oxide, styrene oxide, etc.) is added to this.
They can also be used together. The base polyether preferably has an OH value of 28 to 83 (especially 25 to 67).

The random polyoxyalkylene chain and the terminal polyoxyethylene chain may be directly bonded or may be bonded via the polyoxyalkylene chain -(A20)C-. In the latter case, the alkylene oxide used to form the intervening polyoxyalkylene chain: <A2O> is usually propylene oxide or other algylene oxides (such as butylene oxide, styrene oxide, etc. with 4 carbon atoms). A small amount (for example, 5% or less) of the above-mentioned fulgylene oglyde can also be used in combination.

The proportion of oxyethylene groups in the entire polyether polyol is usually 10 to 40%, preferably 15 to 30%.
It is.

The OII value of the polyether polyol is suitably 20-50, preferably 22-40. When the OH value is less than 20, the viscosity becomes high and flowability becomes poor. In addition, the reactivity with the glycol used in polyurethane molding is not well balanced (difficult to obtain good physical properties). elongation, impact properties, etc.) of the polyether polyol decreases.The number of functional groups of the polyether polyol (
average) is usually 2-6, preferably 2-4. The polyether polyols include two types of polyether polyols with different 011 values (for example, one with an OIII value of up to 50 and one with an OIII value of 50 or more), two or more types with different primaryization rates (for example, 30
% or more and less than 30%), types of raw active hydrogen atom-containing compounds, and two or more types with different numbers of functional groups may be used in combination. The polyether polyol can be used in combination with other polyether polyols (e.g., propylene oxide adducts, propylene oxide/ethylene oxide→noid coadducts (chip type, balanced type, random type)).
You may manufacture a polymer polyol by using it together with. In this case, the polyether polyol usually accounts for 10% or more, more preferably 30% based on the total amount of polyether polyols.
It is appropriate to use % or more. Bo IJ The (average) terminal oxyethylene group content of the entire ether polyol is 8
It is preferable to set the amount to 40%, particularly 10 to 30%. In addition, low molecular polyols (ethylene glycol,
Glycols such as diethylene glycol, polyhydric alcohols such as triethanolamine, and chrycerin) in small amounts (
(usually 20% by weight or less) can also be used in combination.

Examples of ethylenically unsaturated monomers used in the production of the polymer polyol used in the present invention include the following.

(U) Acrylic acid, methacrylic acid and derivatives thereof: acrylonitrile, methacrylonitrile.

Acrylic acid, methacrylic acid and their salts.

Methyl acrylate, methyl methacrylate, dimethylaminoethyl methacrylate, acrylamide, methacrylic acid amide, etc.

(11) Aromatic i-vinyl monomers: styrene, α-methylstyrene, etc.

((d) Claw body for olefinic hydrocarbons: Ethylene.

propylene, butadiene, isobutylene, isoprene,
14-pentagene, etc.

(d) Vinyl ester single jl=: hinyl acetate, etc.

((5) Vinyl halide monomer; vinyl chloride, vinylidene chloride, etc.

(f) Vinyl ether single M3: vinyl methyl ether, etc.

Among these, preferred is acrylonitrile.

These are methyl methacrylate, styrene, and butadiene. Particularly preferred is acrylonitrile, or a combination of acrylonitrile and styrene (styrene:acrylonitrile weight ratio of 10:90 to 60:40). The ratio of the polyol (the polyether polyol and other polyols as necessary) to the monomer in the polymer polyol of the present invention can be varied over a wide range, but usually the ethylenically unsaturated monomer ( or polymer) 2 to 70 parts by weight, preferably 5 to 40 parts by weight.

The production of polymer polyols from polyols and ethylenically unsaturated monomers can be carried out by conventional methods. For example, a method of polymerizing an ethylenically unsaturated monomer in a polyol in the presence of a polymerization catalyst (such as a radical generator) (U.S. Patent No. 8883851, Japanese Patent Publication No. 89-24787,
Japanese Patent Publication No. 47-47999, Japanese Patent Publication No. 50-15894) and a method in which a polymer obtained by pre-polymerizing the above monomers and a polyol are graft-polymerized in the presence of a radical generator (Japanese Patent Publication No. 47-47597). ) can be given. The former method is preferred. As the polymerization catalyst (radical generator) used in the polymerization reaction, azo compounds, peroxides, persulfates, perborates, etc. can be used, but azo compounds are practically preferred. The amount used is not particularly limited, for example, ethylenically unsaturated monomer (or polymer)
100 parts by weight (0.1 to 20 parts by weight, preferably 0
J) at 1 to 15 parts by weight. The above polymerization can also be carried out in the presence of a solvent such as toluene, xylene and the like. The reaction temperature is usually 50-170'C.

Preferably it is 90-150°C.

A polyether polyol obtained according to the present invention having a polyoxyethylene chain at the molecular end and a random polyoxyalkylene chain consisting of an oxyethylene group and an oxypropylene group in the chain, and an ethylenically unsaturated monomer. By reacting with organic polyisocyanate, polymer polyol has fast curing properties, greatly improves the brittleness of the resin, has high initial strength and stiffness, and has excellent temperature characteristics (low temperature and high temperature resistance). (There is little difference in physical properties)
Give polyurethane. Furthermore, the polymer polyol obtained from the present invention has excellent curing properties and requires only a small amount of catalyst, thereby avoiding deterioration in the physical properties and heat resistance of polyurethane due to the use of a large amount of catalyst.

By reacting with an organic polyisocyanate and molding it by the RIM method, the polymer polyol obtained according to the present invention exhibits superior effects in the following points compared to conventional products: ) Since it has excellent curing properties, it is extremely effective in shortening the cycle time from injection to demolding, which is the original purpose of the RIM method.

(2) Even with a small amount of catalyst, it has excellent curing properties, so the increase in viscosity when reacted with polyisocyanate is moderate, and it is possible to avoid insufficient filling and the formation of voids caused by poor flowability in molded products.

(2) It is possible to produce polyurethane with rigidity and to provide a polyurethane molded product with excellent temperature characteristics (less change in physical properties from low to high temperatures).

In the conventional RIM method, a large amount of catalyst is required to improve the curing properties, so the physical properties of the molded product do not deteriorate due to the use of a large amount of catalyst.

(2) Since the polymer polyol easily exhibits rigidity, the amount of chain extender used is smaller than that of ordinary polyether polyols, and the elongation of the molded product is not impaired. It also has the advantage of reducing the amount of expensive isocyanate.

Further, the polymer polyol obtained from the present invention has R
In addition to the IM method, various polyurethane manufacturing methods (foam, elastomer, sealant, coating agent, etc.)
In particular, it exhibits excellent effects in polyurethane manufacturing methods that conventionally required relatively large amounts of catalysts and in polyurethane manufacturing methods that use chain extenders.

The polymer polyol obtained in the present invention can be reacted with an organic polyisocyanate alone or in combination with other polymer polyols and/or chain extenders and crosslinking agents to produce polyurethane. The reaction components used (other polymeric polyols, chain extenders, crosslinking agents) and blowing agents (water and/or fluorocarbons) and other auxiliaries (catalysts,
surfactants, etc.), polyurethane manufacturing methods (one-shot method, prepolymer method, NCO index, molding method, etc.) may be the same as conventional methods, and specifically, the original application, Japanese Patent Application No. 1983-1
This can be carried out by the method described in the specification of No. 02140.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. (The parts shown in the examples are parts by weight.) Example 1 4908 parts of propylene oxide in 92 parts of glycerin,
Next, add ethylene oxide and propylene oxide to 4
100 parts of a polyether polyol with a value of 0.21 obtained by adding 1"600 parts of a mixture at a weight ratio of 0.6 to 6, then 4'00 parts of propylene oxide, and 1200 parts of ethylene oxide were reacted. The temperature was raised to 110-1806C with stirring, and then 0.8% was added as an initiator to a pre-mixed mixture of 10 parts of acrylodisilyl as an ethylenically unsaturated monomer and 10 parts of styrene.
A solution of 50% azohisisobutyronitrile was added dropwise little by little. After completion of the dropwise addition, the mixture was aged at the same temperature for 1 hour to obtain a polymer polyol (1) according to the present invention.

Example 2 4 parts i of 1 g of trimethylolpropane, 3130 parts of propylene oxide, and then 336 parts of a mixture of ethylene oxide and propylene oxide in a weight ratio of 8:2
100 parts of a polyether polyol with a 011 valence of 35 obtained by adding 1200 parts of ethylene oxide,
Polymerization was carried out in the same manner as in Example 1 using a premixed monomer of 16 parts of acrylonitrile and 4 parts of styrene as ethylenically unsaturated monomers and 1.0 part of azobisisobutyronitrile as an initiator. Thus, a polymer polyol (It) according to the present invention was obtained.

Example 3 OI obtained by adding 4072 parts of propylene oxide to 92 parts of glycerin, then 1028 parts of a mixture of ethylene oxide and propylene oxide in a weight ratio of 7:3, and then 900 parts of ethylene oxide. -I
Polymerization was carried out in the same manner as in Example 1 using 100 parts of polyether polyol having a valence of 28, 25 parts of acrylonitrile as the ethylenically unsaturated monomer and 1.0 part of azohisisobutyronitrile as the initiator. , a polymer polyol (lII) according to the present invention was obtained.

Example 4 76 parts of propylene glycol, 2724 parts of propylene oxide, and then 400 parts of a mixture of ethylene oxide and propylene oxide at a weight ratio of 1:1,
Furthermore, 800 parts of ethylene oxide was added to obtain O.
Performed using 100 parts of HHE11 polyether polyol, a premixed monomer of 16 parts of acrylonitrile and 4 parts of styrene as ethylenically unsaturated monomers, and 1.0 part of azobisisobutyronitrile as an initiator. Polymerization was carried out in the same manner as in Example 1 to obtain a polymer polyol (a) according to the present invention.

Example 5 OHH obtained by adding 5612 parts of propylene oxide to 186 parts of pentaerythrol, then 2338 parts of a 1:1 mixture of ethylene oxide and propylene oxide, and then 1400 parts of ethylene oxide.
100 parts of E24 polyether polyol, 16 parts of acrylonitrile as ethylenically unsaturated monomers, and 4 parts of styrene were mixed in advance, and 0.0 parts of monomer was used as an initiator.
Polymerization was carried out in the same manner as in Example 1 using 8 parts of azobisisobutyronitrile to obtain a polymer polyol (V) according to the present invention.

Comparative Example 1 100 parts of a polyether polyol with a hydroxyl value of 34 obtained by adding 4258 parts of propylene oxide and 650 parts of ethylene oxide to 92 parts of glycerin, 16 parts of acrylonitrile and 4 parts of styrene as ethylenically unsaturated monomers. 1 as premixed monomers and initiator
．． Polymerization was carried out in the same manner as in Example 1 using 0 parts of azobisisobutyronitrile to obtain a conventional polymer polyol (
A) was obtained.

Comparative Example 2 100 parts of a polyether polyol with a hydroxyl value of 24 obtained by adding 5928 parts of propylene oxide and 980 parts of ethylene oxide to 92 parts of glycerin, 5 parts of acrylonitrile as an ethylenically unsaturated monomer, and 1.0 parts as an initiator. A conventional polymer polyol (B) was obtained by polymerizing in the same manner as in Example 1 using the azohisisobutyronitrile.

Polymer polyols obtained in the above Examples and Comparative Examples (
Table 1 shows the appearance and analytical values of IV, A, and B).

Using the polymer polyols obtained in the Examples and Comparative Examples shown in Table 1, high-density polyurethane was molded under the following conditions. That is, a polyol component (liquid A) containing a polyol, a chain extender, and a catalyst as main components, and an isocyanate component (liquid B) are respectively charged into a raw material tank of a high-pressure foaming machine, and after mixing liquids A and 13 in a high-pressure foaming machine, Thickness 2, shoulder width 300mm, length 1000mm
Place it in a closed mold where the temperature can be adjusted,
A high-density polyurethane molded product was created.

〔Molding condition〕

Discharge amount (kq 1 minute): approx. 35 Discharge pressure (A liquid/1 monme liquid') (kq/CdO): 180/
150 Injection time (seconds): Approx. 1.8 Raw material temperature (for both A and 13 liquids) ('c): Approx. 40 Mold temperature
("c): Approximately 70 Isocyanate-1... Intex: 105 The molding recipe and the physical properties of the obtained high-density polyurethane are shown in Tables 2 to 4. The molded polyurethane was measured after being left to stand under the following conditions. Nos. 1 to 5 in Table 2 were tested at least 1 week after mold release, and Nos. 5 to 10 were tested at 120 m after mold release.
After annealing at °C for 1 hour, the samples were left at room temperature for 3 days or more and then measured.

Note) The components, mold release time, and physical properties in the table are as follows.

Daiflon-11u: Tigin-ti[[Freon-1106 Black I・su]: Carbon fluff is dispersed in polyether polyol.

DABCO33LV: Amine catalyst manufactured by Sankyo Air Products.

DTD: Shiftirtin dilaurate.

Millione-1-MTL: Modified MDI manufactured by Nippon Polyurethane Co., Ltd. Mold release time: Time from the time when the liquid starts to be poured into the mold until it is taken out.

Initial strength: Immediately after the molded product is released from the mold, a sample for tensile strength measurement is punched out using a dumbbell.

Next, this sample was released from the mold for 60 minutes. Measure the tensile strength at the moment of the first period intensity.

Bending modulus: Sample size; 25 mm
Measured at X'10mm x 2.5mm (1,) span 40mm.

Heat Sag: Sample size 25+avX150
After leaving it at 120°C for 1 hour with iyz

Embrittlement temperature: According to 1ISK-6801.

Water absorption rate: Sample size 1O+, wX22
Weight change rate after immersion in a water tank at 40°C for 10 days.

Table 3 Physical properties Table 4 Physical properties (c)

Claims (1)

[Claims] 1. In producing a polymer polyol from a polyol and an ethylenically unsaturated monomer, as the polyol,
1. A method for producing a polymer polyol, which comprises using a polyether polyol having a polyoxyethylene chain at the molecular terminal and a random polyoxyalkylene chain consisting of an oxyethylene group and an oxypropylene group at the non-terminal end. 2. The method for producing a polymer polyol according to claim 1, wherein the polyoxyethylene chain accounts for 8 to 80% by weight of the total molecular weight. 3. The random polyoxyalkylene chain has an oxyethylene group and an oxypropylene group in a weight ratio of 90:10 to 30.
A method for producing a polymer polyol according to claim 1 or 2, which has a molecular weight of 70% to 5% to 25% by weight of the total molecular weight. 4. The random polyoxyalkylene chain has a total molecular weight of 6
A method for producing a polymer polyol according to claim 1.2 or 3, wherein the polymer polyol is located at the end of 0%. 5 The polyether polyol has a functional group number of 2 to 6 and OH
A method for producing a polymer polyol according to any one of claims 1 to 4, which has a valence of 20 to 50.