JPH02501145A - Polyurethane elastomers from EO/BO polyether polyols - 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] Polyurethane elastomers from EO/BO polyether polyols The present invention relates to polyurethane and/or polyurea elastomers. More details In particular, the present invention relates to a copolymer of ethylene oxide and butylene oxide containing active hydrogen. Regarding polyurethane and/or polyurea elastomers manufactured from Ru.

Polyurethane and/or polyurea are polyisocyanates and polyols. It is commonly prepared by reacting with polymers and "chain extenders". polyol is an alkylene oxide, epihalohydrin, tetrahydrofuran or similar compound by reacting the compound with an initiator to form a hydroxyl-terminated polyether. It is a commonly produced polyether.

This polyether can, if desired, be an amino-terminated polyether. can be aminated to provide

Chain extenders are relatively low equivalent weight compounds that contain groups that can react with polyisocyanates. be.

The most commonly used polyether polyol is a polymer of propylene oxide. . However, there are certain advantages to using poly(ethylene oxide) polyols. Recognized. In particular, poly(ethylene oxide) polyol has an elastomer with high tensile strength. If the crystallization stress is increased, crystallization stress can be applied.

Unfortunately, poly(ethylene oxide) polyols are unsuitable for elastomer production. It has some very important drawbacks. Most importantly, ethylene oxide poly This means that the mer is very hygroscopic. manufactured from these polyols The elastomer is therefore very water sensitive and should not be exposed to any humidity or aqueous rings. It cannot be used even in the border.

In addition, poly(ethylene oxide) polyols often have moderate tear strength. Forms an elastomer with poor elastomer properties.

Poly(acid) is produced by copolymerizing ethylene oxide (EO) with high alkylene oxide. Attempts have been made to obtain some of the advantages of polyols. polyol Although the presence of high alkylene oxide units in the Allows for some advantages. Generally, alkylene oxide copolymerized with EO is an oxidized product. It is pyrene (PO).

In U.S. Pat. No. 4,301.110, EO and butylene oxide were used as polyols. Producing polyurethane elastomers using copolymers with BO is taught. These polyols are initiated by a mixture of EO and BO. co-react with the copolymer and then add EO to the copolymer to “cap” Manufactured by. Use of this polyol provides improved heat distortion and tear properties It is said that it will. However, these elastomers have very low tear properties. have It exhibits excellent tensile and tear properties and is superior to conventional poly(EO)-containing polyols. polyols made from EO-containing polyols that are less sensitive to water than those made from It would be desirable to provide urethane and/or polyurea elastomers .

The present invention relates to polyurethane and/or polyurea produced by the reaction of: It is an elastomer.

a) Organic polyisocyanate b) a chain extender and C) poly(BO) blocks comprising 10-90% of the total polyether weight oxidation comprising an internal poly(EO) block to which said poly(BO) block is bonded. Block copolymer of ethylene and butylene oxide, molecular weight 500-10 ,000 isocyanate-reactive polyether.

The elastomers of the present invention have excellent tear strength. The tear strength of this elastomer is , generally produced using EO or BO homopolymers as polyols larger than that of similar elastomers. This elastomer is also highly resistant to organic solvents. It is durable and has good tensile properties. Surprisingly, poly(EO) polyol Substantially reduces water sensitivity in comparison and is therefore useful in general applications requiring moisture tolerance. .

The elastomers of the present invention are organic polyisocyanate, chain The reaction mixture consisting of the extender and the EO/BO block copolymer is reacted together. It is manufactured by making it correspond.

The EO/BO block copolymer used here has multiple active hydrogen-containing groups. , molecular weight 500-10.000, preferably 600-8000, more preferably 750 to 5000;

The copolymer also has an internal polyester bonded to poly(BO) blocks 110 on both sides. It is characterized by containing (EO). When determining the relative position of blocks The presence of any initiator compound is ignored. EO/BO block copolymer contains 10-90% by weight poly(BO) block and at least 10% by weight poly(BO) block. (EO) block.

The internal poly(EO) block advantageously has a "molecular weight" of 200 to 5000, preferably preferably 400 to 3000, more preferably 600 to 2000. The internal EO The number of poly(BO) blocks bonded to the block is from 10 to 90, preferably from 20 to 75, more preferably 30 to 65% by weight of Sibutylene units containing EO/ Such as BO block copolymer. The BO block is a small amount, 30 Randomly copolymerized epichlorohydrin or trichlorb oxide up to % C3 or higher alkylene oxides or internally substituted C3 such as tyrene or higher alkylene oxides.

The block copolymers useful here are, in their simplest case, represented by the structure: I can do it.

where A is the active hydrogen-containing moiety, In is the residue from the polyvalent initiator, and R is hydrogen, halogen or an internally substituted alkyl group, and 2 is 2-8, preferably Preferably, the number is 2 to 4, more preferably 2 to 3, and X and n are block copolymer. The remer has a poly(BO) content as described herein. these In addition to simple block copolymers, multiblock copolymers such as those represented by the structure Quercus copolymers and similar structures exist.

RC2H5CZ)15 where m, n, x and y are block copolymers such as poly(B) as described herein. O) is a number having a content rate, and A, R and 2 are as described above. requested In addition to the EO and BO blocks, poly(BO) and poly(EO) inclusions If as described here, other alkylene oxides and/or randomly separated Cells containing dispersed oxybutylene, oxyethylene or other oxyalkene units It is further within the scope of the present invention to use polymers containing blocks of be.

Block copolymers of structure I are advantageously prepared until the desired molecular weight is obtained. React ethylene oxide with polyvalent initiator, then react polyether with butylene oxide Manufactured by If R is not -CH2CH3, polyether The tel is then reacted with a suitable alkylene oxide. In such a case, A is a hydroxyl group Will. Other groups such as amino groups can be introduced by reductive amination using known methods. I can do it. Structure ■−■ similarly corresponds to the sequential addition of alkylene oxide to the initiator compound. Manufactured by

A suitable initiator compound reacts with the alkylene oxide to open the oxirane ring. Contains low equivalent weight polyols, polyamines and other compounds with multiple active hydrogen atoms. nothing. Such typical compounds are described in U.S. Pat. No. 4,500 to Meyer. ．． It is described in No. 442 No. 2@. Particularly suitable initiators are 02-C6 alkylene Glycol, CZ~C, alkylene diamine, bisphenol, aminoethyl diamine perazine, e.g. tripropylene glycol, diethylene glycol, dipropylene glycol Di- and trialkylenes such as lene glycol and triethylene glycol Contains glycol.

Methods for polymerizing alkylene oxides in the presence of polyvalent initiators are well known, e.g. Described in US Pat. No. 3,040,076. Generally, alkylene oxide is , in the presence of an initiator using a strong base such as an alkali metal hydroxide as a catalyst. Polymerization is carried out at pressures above atmospheric pressure. Form a terminal poly(BO) block Polymerization of BO produces terminal secondary hydroxyl groups. more reactive groups such as primary hydroxyl or amino groups. It is often possible to increase the reactivity of polyols by introducing reactive groups. Often desired.

Primary hydroxyl groups are most quickly removed by capping the polyol with ethylene oxide. will be introduced in Amino groups can be used as described in U.S. Pat. No. 3,654,370. It can be added by reductive amination. primary hydroxy and/or Mono- or secondary amine-terminated polyols can be added to -11Ei by reaction injection synthesis. (RIM) method is preferred.

Chain extenders are used in making the elastomers of this invention. “Chain extender” The term is used here to refer to relatively low equivalent weight compounds with multiple active hydrogen atoms (i.e. 250 equivalents or less). Polyurethane and/or polyurea elastomer The use of chain extenders to prepare polymers is known in the art. Appropriate Chain extenders include low equivalent glycols, low equivalent alkylene diamines, aromatic diamines, including mixtures thereof and analogues thereof. A suitable chain extender was given by Meyer Rice contains ethylene glycol, l,2-propylene glycol, and 1,4-butylene glycol. diol, dipropylene glycol, diethylene glycol, diethyl toluene diamine, methylenebis(0-chloroaniline), ethylenediamine and hydrogen and/or blocked aromatic diamines.

The amount of chain extender used will vary depending on the desired physical properties of the elastomer. Change. Higher proportion of chain extender gives stronger stiffness and higher heat deflection Provides an elastomer with temperature. Lower amounts of chain extender result in more flexible Provide lastomers. In particular, 2 to 70, preferably 10 to 40 parts of chain extender is used per 100 parts of polyol.

Organic polyisocyanates are also used to make the elastomers of the present invention. . Suitable polyisocyanates include aliphatic polyisocyanates as well as aromatic polyisocyanates. Contains 1-socyanate. Such polyisocyanates are described, for example, in U.S. Pat. No. 4.065.410, No. 3,401,180, No. 3.454,606, No. No. 3.152.162, No. 3,492,330, No. 3,001,973, No. No. 3,394,164 and No. 3,124.605.

Aromatic polyisocyanates useful herein include 2,4- and/or 2,6- luene diisocyanate, p,p'-diphenylmethane-diisocyanate (M DI), P-phenylene diisocyanate, polymethylene polyphenyl polyester including socyanates, mixtures and analogs thereof. Also useful are those Polymerization of p,p'-diphenyl-methane diisocyanate as well as quasi-prepolymer It is a conductor. A useful aliphatic polyisocyanate is hexamethylene diisocyanate. isophorone diisocyanate and 1,4-cyclohexane diisocyanate nates as well as hydrogenated derivatives of the previous aromatic polyisocyanates.

In addition, the previous polyisocyanate with -NGO content of 0.5 to 32% by weight Prepolymers and quasi-prepolymers are useful here. Such prepolymer Using - is preferred for -JG. Preferably, the prepolymer weighs between 2 and 25 wt. % of isocyanate groups, more preferably 4 to 18% by weight of isocyanate groups. have These prepolymers contain more than the stoichiometric amount of polyisocyanate with active hydrogen. It is readily produced by reacting with the contained substances. Active hydrogen-containing substances are highly or can be of low equivalent weight. The active hydrogen-containing substance is the block used here. It can be the same or different from the wolfberry copolymer.

However, 1 millimer is a block copolymer with a total or partial block copolymer and an excess of polymer. Preferably, it is produced by reacting a liisocyanate. This prepo The reamer is then reacted with a chain extender and the total remaining amount of Pronk copolymer. . However, so-called “one-shot” processes that do not involve the use of prepolymers It is noted that is appropriate here.

Particularly preferred are those having a molecular weight of 600 to 2000 and a BO content of 30 to 65%. alkylene glycol or di- or tri-alkylene glycol block copolymers with chain extenders and MDI or hydrogenated MDI. It is an elastomer manufactured from

For example, additives such as catalysts, blowing agents, surfactants, fillers and pigments may be added to the present invention. It can be used to produce bright elastomers. The use of such additives is a traditional technique. It is known in the art.

Suitable catalysts include tertiary amino acids such as those described in U.S. Pat. No. 4,065,410. including organic compounds and organometallic compounds. The use of such catalysts is advantageous for the elastomers of the present invention. preferred for making. Generally, 100 parts of polyol is used to make an elastomer. From 0.10 to 1 part of catalyst per liter is used. Foamy and/or low density foam The blowing agents used to make lastomers are water and low-boiling halogenated alkalis. methane, especially chlorinated and/or fluorinated methane.

Suitable pigments and fillers include carbon black, titanium dioxide, iron oxide, carbonate Calcium, alum, kaolin or wollastonite-like viscosity. Pudoglass fiber, continuous glass fiber, flake glass, polyester and other polymeric fibers.

The elastomers of the present invention can be manufactured using various process techniques to produce elastomeric products. can be prepared from the ingredients described above. For example, this elastomer It can be manufactured using the known reaction injection molding (RIM) technology. Ru.

However, the elastomer of the present invention is preferably a cast elastomer. mosquito Cast elastomers such as mixed at high temperature and then heated in a mold to form the elastomer into the desired shape. Manufactured by molding under pressure. As discussed earlier here, The lysocyanate is then treated with a preform that is reacted with the remaining isocyanate-reactive material. one or more isocyanates to form a polymer or quasi-prepolymer. can be pre-reacted with a nate-reactive substance. Cast elastomer formed Appropriate curing conditions when °C temperature and a curing time of 10 minutes to 3 hours, preferably 15 to 30 minutes. R.I. When M processing is done, the curing time in the mold is especially 30 seconds to 1 hour. be. This is often followed by post-curing outside the mold. However, the optimal curing conditions is the special ingredient used to make elastomers and molded from it. It is understood that this will depend on the size and shape of the product.

The elastomer of the present invention can be used, for example, in rollers, hammers, pipe liners, gears, etc. , pump room, wheels, impellers, door seals, coatings, tires, wiper blades, gas Useful in manufacturing products such as skets and belts. To make such a product , block copolymers such as polyether polyols and polyesters It can be blended with other active hydrogen containing materials such as polyols.

The following examples are provided to illustrate the invention but do not limit the scope of the invention. It's not a thing. All parts and percentages are by weight unless otherwise specified.

■D A series of elastomers are now combined to form a 12% NCO prepolymer. 100 parts by weight of a polyol as described in CMDI). The prepolymer is a polyol The mixture was formed by heating the MDI and MDI together at 90° C. for 30 minutes.

After cooling the prepolymer to room temperature, the prepolymer is degassed and the 1,4-butanedio blended with The ratio of prepolymer to 1,4-butanediol is , the ratio of isocyanate groups to hydroxyl groups is 1.05 (105 index). It was like that. Next, 1.3 d of organic mercury catalyst was poured into the solution while stirring under vacuum for 30 seconds. and the mixture was pretreated with a mold release agent and heated to 150"C. "X 6" X 1/8" (1521WIX 152 body x 3, 2mm ) was placed in a mold. The mold costs 10,000 pounds (69,000k) for 30 minutes. Pa) (7) Heated to 150″c under applied pressure.

In comparison sample A, the polyol used to produce the x-y stomer was was a poly(oxyethylene) diol with a molecular weight of 1000 (Polyol A) .

In sample 1, the polyol was polyol A with butylene oxide up to a molecular weight of 1200. BO/EO/BO block copolymer produced by reacting with (Polyol B).

In sample 2, the polyol is polyol A with butylene oxide up to 1t1344 molecules. BO/EO/BO block copolymer produced by reacting with (Polyol C).

In sample 3, the polyol is polyol A with butylene oxide up to a molecular weight of 1500. BO/EO/BO block copolymer produced by reacting with (Polyol D).

In sample 4, the polyol is polyol A with butylene oxide up to a molecular weight of 1800. BO/EO/BO block copolymer produced by reacting with (Polyol E).

In sample 5, the polyol is polyol A with butylene oxide having a molecular weight of 266°. BO/EO/BO block copolymer produced by reacting with (Polyol F).

Each elastomer sample number 1-5 and comparative sample A were tested for tensile and bending. The tear properties, tear strength, hardness, glass transition temperature and moisture sensitivity were measured. Go The tests conducted and the results of such tests are as shown in Table I. Result is Reported as the average of double molding results.

〉 □ As can be seen from the data in Table 1, the presence of poly(BO) blocks in polyols is , provides a substantial reduction in moisture sensitivity and provides a significant improvement in tear strength. . The tear strength data is significant and shows improved moisture resistance. In the sample of the present invention Flexural modulus and, with one exception, elongation showed significant improvements. comparison sun Despite having the highest dry box tear strength, Pull A It showed a substantial loss in tear strength when exposed to water. However, sample 1 -5 generally did not show such a large loss in properties. This means that Shows no substantial decrease in tear strength when exposed to atmospheric moisture This was especially true for sample numbers 2-4.

Banmata Comparative sample B and sample number 6-8 were prepared using the following polyols: was prepared according to the general method described in Example 1, with the following exceptions:

In comparative sample B, the polyol was poly(oxyethylene) with a molecular weight of 1400. (Polyol G).

In sample 6, the polyol was oxidized to polyol G to a molecular weight of 1900. BO/EO/BO block copolymer produced by reacting with tyrene (Polyol H).

In sample 7, polyol G was oxidized to a molecular weight of 2200. BO/EO/BO block copolymer produced by reacting with tyrene (Polyol ■).

In sample 8, polyol G was oxidized to a molecular weight of 2600. BO/EO/BO Pro-Nc copolymer prepared by reacting with (Polyol J).

The elastomer was tested as described in Example 1 and the results are shown in Table H. It was close.

Split tear, pli (kN/m) 3150 (26,3) N, 0. 1 89 (33,1) 154 (27,0) Moisture absorption (%) S40.4 33.7 2 7.5 21.58 This is not an example of the present invention.

N, D, - Not detected.

'Tensile and elongation dry box test determined by ASTM D-412 with 0% phase Tests were carried out on samples kept at relative temperature for 7 days. Immersion tensile test is ASTM D- 471 was carried out on samples immersed.

” ASTM D-790 3ASTM D-470C ' ASTM D-2240 ' ASTM D-471 Reduced moisture sensitivity and improved tear strength were observed with examples of the invention. Poly (BO) An increase in flexural modulus and elongation with increasing content was also observed. tensile strength and The increase in flexural modulus with increasing elongation was considered surprising.

Master Sample numbers 9-11 were manufactured and tested in the following general manner as described in Example 1. It was written. The polyols used were as follows.

In sample number 9, the polyol is poly(ethylene oxide) with a molecular weight of 2000. Produced by reacting diol with butylene oxide to a molecular weight of 2500 It was a BO/EO/BO block copolymer (Polyol K).

In sample 10, the polyol is polyethylene oxide oxide with a molecular weight of 2000. It was prepared by reacting the compound with butylene oxide to a molecular weight of 2800. B.O. /EO/BO block copolymer (Polyol L).

In sample 11, the polyol is polyethylene diol oxide with a molecular weight of 2000. BO/ It was an EO/BO block copolymer (Polyol M).

The results obtained in testing these elastomers are as reported in Table 3.

Hawk knee l Polyol K L M Molecular weight 2500 2800 3200 Perimeter elongation %' 550 610 68 0 shore-A hardness' 85 88 90 Tg ("C) -20-36-3'5 Moisture absorption (%')' 38.3 32. 0 29.7N, D, not detected 'Tensile and elongation dry box test determined by ASTM D-412 with 0% Performed on samples kept at relative humidity for 7 days. Immersion tensile test is ASTM D -471 on samples immersed.

2 Eight STM D-790 38 STM D-470C ' ASTM D-2240 ' ASTM D-471 Again, improved tear strength, flexural modulus, elongation and moisture resistance were observed in the inventive samples. It was seen.

Nuki↓ Polyol E is a mixture of 2,4- and 2,6-toluene diisocyanates. It was reacted to give -NGO prepolymer in 7.4% yield. This reaction blocks the components. This was done by blending and heating at 70°C for about 30 minutes. The resulting prepo Rimmer is 105 index (index = 100X (number isocyanate methylene oxide by the method described in Example 1, in proportions providing was reacted with Nbis(0-chloroaniline). The resulting elastomer is It was named pull number 12.

This experiment was repeated, this time using a prepolymer containing 9.6% -NGO. It was done. This elastomer was designated sample number 13. Sample number 12 The properties of and 13 are as reported in Table 3.

steal 22 dents Polyol E E Molecular weight 1800 1800 NC0% in prepolymer 7.4 9.6 Elongation, %' 468 291 Shore-A hardness 391 91 Tg (”C) -24-26 ' ASTM D-412 ” ASTM D-470C ' ASTM D-2240 The polyol is poly(oxybutylene) diol with a molecular weight of 250 and a molecular weight of 1850. By reacting with ethylene oxide up to the molecule t3250 and then with butylene oxide up to the molecule t3250. Manufactured by. A prepolymer containing an NCO content of 11.9 1101 as described in Example 1. child The prepolymer of forms an elastomer (sample no. 14) with the following properties: In order to It is made to react with

Tensile strength, psi (MPa)' 3595 (24,8) Elongation, %l326 Split tear, pli (kN/+n)” 175 (30,6) Beashore -(Bashore) Elastic rebound 323 Shore-A hardness 487 Tg, °C-20 ' ASTM D-412 ”AST?l D-470C ” ASTM D-2632-79 48 STM D-2240 ■yo The O/EO/BO block copolymer is a poly(oxyethylene) with a molecular weight of 1000. ) Manufactured by reacting diol with butylene oxide up to a molecular weight of 2000. (Polyol N). A portion of this copolymer then has terminal primary amino groups. (polyamine A). 30% by weight polya A mixture of Min A and 70-weight polyol N has an NCO of 11.7%. by the method described in Example I to form a prepolymer with MDI. I was made to do it. This prepolymer is an elastomer with a 105 index and the following properties: 1,4- as described in Example I to provide the tomer (sample no. 15). Reacted with butanediol.

Tensile strength, psi (MPa)' 3763 (25,9) Elongation, %1354 Split tear, pli (kN/m) 2236 (41,3) Compression set 3 12 Shore A hardness '89 Tg, “C-14 % Moisture absorption amount 54 ' ASTM D-412 2ASTM D-470C 3ASTM D-395 'AST Month D-2240 5AST? ID-471

Claims (10)

[Claims] 1. Polyurethane and/or polyurea elastomer produced by the reaction of: Tomer. a) Organic polyisocyanate b) a chain extender and c) Both poly(BO) blocks account for 10-90% of the total weight of the polyether. an acid comprising an internal poly(EO) block whose sides are bonded to said poly(BO) block; A block copolymer of ethylene oxide and butylene oxide, with a molecular weight of 500 to 1. Isocyanate-reactive polyether with 0,000. 2. Claim 1 wherein said polyether contains 30 to 65% by weight of oxybutylene moieties. Elastomers listed. 3. The polyether has an internal EO block with a molecular weight of 600 to 2000. The elastomer according to claim 2. 4. The elastomer according to claim 3, wherein the chain extender comprises an aromatic diamine. 5. Polyisocyanate is aromatic polyisocyanate or aliphatic polyisocyanate. The elastomer according to claim 3, which is an anate. 6. The elastomer of claim 1, wherein the polyether has the structure: ▲There are mathematical formulas, chemical formulas, tables, etc.▼In formula (I), A is an active hydrogen-containing moiety, R is an internally substituted alkyl group or hydrogen, and In is an internally substituted alkyl group or hydrogen; residue, z is a number from 2 to 4, and x and n are polyethers from 20 to 75. Such a number has a poly(BO) content of % by weight. 7. 2. The polyether according to claim 1, wherein the polyether is represented by structure II, III or IV. Elastomer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) In the formula, A contains active hydrogen , In is the residue from the polyvalent initiator, z is a number from 2 to 4, and R is an internally substituted alkyl group or hydrogen, and x, y, m and n are The number is such that the copolymer has a poly(BO) content of 20 to 75% by weight. 8. Polyurethane and/or polyurea, including reacting with: Method for producing lastomers. a) Organic polyisocyanate b) a chain extender and c) Poly(BO) blocks account for 10-90% of the total weight of the polyether Contains an internal poly(EO) block joined to said poly(BO) block on the side Copolymer of ethylene oxide and butylene oxide, molecular weight 500-10,0 Isocyanate-reactive polyether with 00. 9. 9. The method of claim 8, wherein the polyether has the structure: ▲There are mathematical formulas, chemical formulas, tables, etc.▼In formula (I), A is an active hydrogen-containing moiety, R is an internally substituted alkyl group or hydrogen, and In is an internally substituted alkyl group or hydrogen; residue, and z is a number from 2 to 4. 10. Claims in which the polyether is represented by structure II, III or IV: 8. The method described in 8. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) In the formula, A contains active hydrogen , In is the residue from the polyvalent initiator, z is a number from 2 to 4, and R is an internally substituted alkyl group or hydrogen, and X, y, m and n are The number is such that the copolymer has a poly(BO) content of 20 to 75% by weight.