JPS59500820A - Polyether polyurethane elastic body - 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] Polyether polyurethane elastic body Technical field The present invention relates to the production of elastic non-polyurethane compositions. More particularly, the present invention provides Controlled amounts of polytetrahydrofurandiol in a special molecular weight range terdiincyanate, followed by diamine spreading. Growth of bending cracks and cuts produced by reaction with chaining agents Polyurethane with improved resistance to.

Background technology When polyurethane elastic material bends or bends, it may break or grow cuts. Many attempts have been made to improve its resistance to. however, Improvements in such properties generally include other properties such as tensile strength and modularity. accompanied by loss of strength.

U.S. Pat. No. 3,798,200 discloses that diincyanates such as toluene diisosilane Anate has an average molecular weight of 4000 to 20000 and has a small amount in the molecular weight distribution curve. It has at least two peaks, and at least one of these peaks is a polyether polymer. polyesters in the low molecular weight range and at least others of the peaks are in the low molecular weight range. It is said that polyurethane elastomer is produced by reacting with ester glycol. It claims a method for improving resistance to crevice growth and cracking due to bending.

The same patentee, who recently obtained U.S. Patent No. 3963.681, has a bifluorescent average molecular weight in the range of 1000 to 4500 and has at least two peaks. The molecular weight distribution curve has a molecular weight distribution curve with a Polyethers with at least one peak in the high part of this range Producing polyurethane from polyglycol prevents growth and whitening in cuts. The patent claims improved resistance to cracking.

Molecular needle bunwaku is described above, but Sasa's example uses polyether. The glycol typically comprises a mixture, e.g. one polyether glycol. has a weight molecular weight of 8,500-11,000 and accounts for a fraction of all the glycols present. in such a proportion that the average molecular weight of the mixture as a whole is 4500 or less. Which indicates that.

The patent holder is responsible for the manufacturing process, ((Z) polyether diol or polyether diol) The process involves reacting polyglycol simultaneously with a polyfunctional incyanate and a curing agent. or (b) first reacting a polyfunctional incyanate with a polyether. A prepolymer is produced by reacting with a mixture of glycols, and then this prepolymer is It is described as a two-step reaction in which a hardened elastic body is produced by reacting with a hardening agent. Ru.

However, it is still possible to overcome bending failure without sacrificing other physical properties. Greater improvements in resistance to cut growth are desired.

detailed famine According to the present invention, it is possible to prevent breakage and cutting due to bending without sacrificing the physical strength of the father-in-law. Further improvements to the growth of eyes were first made using polyether glycols or diols. IAfM one diincyanate preformer of the Anate polyether prepolymer (C further polyether glycol also 7% Graded by adding IJ ether glycols and simultaneously reacting with a curing agent It can be completed by manufacturing an exogenous body.

i.e. prepolymer, further polyol and curing agent, once the mixture is cured. When VC reacts. This diincyanate polyether prepolymer is advantageously It has a number average molecular weight of about 800 to 25θ0, preferably about 100 to 2500. . Soyisocyanate preformers, such as toluene diisocyanate 2 moles of aromatic soisocyadiate and a polyether glycol or diol, preferably or from one of the polyether glycols by reaction of polyether diols. The coating is made of a hard polyether diol with a number average molecular weight of about 1000 to 4000. Cured by addition and simultaneous curing with agents such as aromatic polyamines This provides an apparent improvement when producing elastomeric bodies. polyether diincyane The prepolymer is preferably a combination of prepolymer and polyether diol. About 85 to 95 parts by weight, preferably 87 to 92 parts based on 1100 parts, or 5 to 15 parts, preferably 8 to 13 parts of the ether diol. Yoshi The aromatic polyamine curing agent is preferably used in a proportion of flIO to 20%, depending on the equivalent weight. used to advantage. Preferably, the equivalent ratio of active hydrogen in the curing agent is 09-12 divisions per incyanate group.

For use in producing polyether diol diincyanate prepolymers or as a diol added to diincyanate prepolymers. A suitable polyether diol or glycol of formula %formula% [In the formula,) 7° is a carbon number of 2 to 10. Preferably 2 to 6 aliphatic groups.] Polyether diols derived from glycols or corresponding alkylene oxides Including files. These polyether glycols or diols have the formula %formula%) where X is an integer of sufficient value to give the aforementioned molecular weight. the A typical B0 group of the Q+) ether is -C1i2CM2-1-CH2CR2 CH2-, -CB　((,'E,)CB2-,-　(C″B2)4-　;　-C M (CEs)CB2”2-;-(CB2)a-;-(CB2)a -i　-CM　(C3”7)　CH2-;-CB　(C1i,)CB2C1l　 (CB3) - Contains spring. A preferred B0 group is 1,4-butylene diol or tetra Found in polymers derived from methylene glycol and tetrahydrofuran. (C, #2)+-.

Suitable aromatic diisocyanates are, for example, tolylene-2,4-diisocyanate. , tolylene-2,6-diisocyanate, naphthalene-1°5-diisocyanate diphenyl-4,4'-diincyanate, benzophenone-4,4'-diincyanate Incyanate, diphenyl ether or diphenyl sulfide-4,4'- Diisocyanates and their substituted with alkyl, alkoxy, halogen or nitro groups derivatives such as 3,3-dimethyldiphenyl-4,4'-diisocyanate or 3,3'-dichlorodiphenylmethane diincyanate, mixtures thereof Including.

The following diisocyanates are suitable Dorylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, Naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate 3,3'-dimethyldiphenyl-4,4'-diisocyanate, diphenyl Nylmethane-4,4'-diisocyanate, 3゜3'-dichlorodiphenylmeth diincyanate, 1,6-hexamethylene diisocyanate, l,3- and 1.4-Cyclohexyl diisocyanate, methylenebis(4-cyclohexyl diincyanate), and 1,3- and 1,4-xylene diisocyanate. child Mixtures of two or more of these diincyanates can also be used.

Suitable curing agents for use in the present invention include U.S. Pat. No. 4,075,150, 3.9 No. 00,447, No. 3.899,438 and No. 3.876.604. including aromatic polyamines and polyols such as

Suitable aromatic polyamines include, for example, 4,4'-methylene-dianiline, methyl Renbis (ortho-chloroaniline), 2.2', 5-trichlor-4,4' -methylene dianiline, naphthalene-1,5-diamine, ortho-, meta- and hydrogen Paraphenylene diamine, tolylene-2,4-diamine, dichlorobenzidine , diphenyl ether-4,4'-diami [wherein R is -C'B3, -C21] 15-1-c, h7, - C4B9, '8Bl? , CM.

Is it a group consisting of -CM2CM and -C1i (C1i3) -(CB2)3CM3? selection allowance CB3 and R' represents -H1-C'l13, -C,H, and -C6 E, represents a group selected from the group consisting of 3] min, and [wherein J(/ is -C1i3, -C,H,, -(':'B2)2CE s, -C, Bo, C1l.

C’E3 - Selected from the group consisting of C2B, -C3H, -C41f, and Nologon residues. represents the selected group] and derivatives and mixtures thereof.

Preferred polyamines are methylenebis(orthochloroaniline), 4,4'-methylene dianiline, naphthalene-1,5-diamine, ortho-, meta- and hyperaf enylene diamine, tolylene-2,4-diamine, dichlorobenzidine, and especially in complexes with alkali metal halides such as sodium chloride, for example in a ratio of 3:l. It is a methylene dianiline complex.

Suitable polyols include No. ethylene glycol, 1,2- and 1.3-propanol. Pyrene glycol, 1I3- and 1,4-butanediol, bentanediol, hexanediol, decanediol, dodecanediol, trimethylol propane castor oil, glycerin, pentaerythritol, sorbitol, 4.4'- Dihydroxydiphenylmethane, resorcinol, thioglycol and the following formula [formula (n is the carrier number from 1 to 4) and mixtures thereof.

Diols are preferred; among these are ethylene glycol, 1,3-propylene Glycols such as lene glycol, 1,3- and 1,4-butanediol, and There are also a combination of these. High molecular weight diol, for example, product name "po14ym" Polytetrahydrofuran (THF) diol, commercially available as be.

The number of active hydrogen equivalents of the polishing/curing agent per inanate ticket is preferably 0.9 to 1.2. Preferably, it is selected from the range of 0.95 to 11.

When producing polyether diisocyanate prepolymers, diisocyanate Standard equipment with suitable stirring means suitable for the reaction with diols of used. For the reaction with polyether diol, similar equipment or similar equipment is used. One device may be used. For reaction with hardeners, the hardened elastic product is Any suitable molding equipment may be used for molding.

There are many commercially available products that may be used as components to the methods and products of the invention. exist. For example, polyethers with diisocyanate end groups may be Polytetrahydrofuran (polyTEF) with rearranged isocyanate end groups is commercially available under the trade name "Adiprene".

A particularly suitable curing agent is also commercially available under the name "Caytur".

For example, Caytur 21'' has 3 moles of methylene dianidine per i mole of IvaCl. 49.5% dioctyl phthalate of sodium fluoride complex of phosphorus (1) UP>min Contains a dispersion. The complex is cured at an elevated temperature, advantageously at least 100 °C, preferably at least 120 °C, so that premature curing does not occur. Therefore, it is suitable.

The ingredients can be added sequentially with the minimum addition of 1 toluene diisocyanate. . After proper stirring, the mixture is poured into a heated mold and the temperature is increased to activate the complex. It can be raised to a suitable extent to function as a curing agent.

Tecrbs Flew, used to measure cut growth and various physical properties. The methods used are those commonly used for such purposes. If it is IJ, it will be tensile. For resistance, see ASI'M Test Method/)-638.

Example The following examples illustrate the method of the invention. These examples represent the best examples currently known. Including examples, it is not intended to illustrate merely any way in which the invention may be practiced. However, the scope of the present invention is not limited to the embodiments thereof. Unless otherwise specified, Parts and units are indicated as parts by weight and units are indicated as parts by weight, and the number before the molecule is the number average molecule. It's the amount.

In these examples, the various materials referred to in terms of end groups and molecular weights are Product names such as those shown in the mark may be displayed as follows: (a) Molecular weight 1320, /V CO terminal polyTIIF is #C (J6.4% 'Adiprene' has a molecular weight of 2oo PolyTHFId at the tvco end of o, IvCO4, Liof:TiS:):r″ Adiprene　”　L　-100; (c) Molecular weight a　o　o　oo PolyTl1F at the end of 7vco is adiprene"L- It is 42; (d> The NCO-terminated polyTHF of the molecule 1i5600 is a laboratory-produced material. be; (e) The polyTHF at the IiO end of molecule 1loooo has a number of 1145 molecules in human Ooxy. Polymeg is 1000; PolyTBF is "Polymeg" 2000 with human number 577; ((7) PO+ at the BO end of the molecule ffi s o o o o) THF is bitroxy Po11meg' 5000 with 21.6 files: (h) Toluene diisocyanate (TDI) is “Hyle’ne”; and (Z) A 49.5% dispersion of NaC1 anchor of methylene dianiline (MDA) is 1) It is commercially available from Upont under the trade name wCαyhbr-2'l". Dioctylphthalate (D Op) Medium B/V a CL ・3 (MDA) There is.

Summer list (Nli2+0R)lIVCO ratio -1,0251,0251,025IVH2 /IVCO ratio 1.025 Table 1 Busy 110 terminal Boria” II F electric combination Molecular weight 1000 ((7Hit 14.5) z.

molecular needle 2000 (Uli number 58.7) 10 Molecular weight 5000 (Number of OBs 21.6’) 9.2 toluene sulfur Anate (1’DI) 3,54 1,77 1.72ba αCt・3MI)A Dispersion of 34.3 39.0 36.8 37.9 DOP 6 6 6 6. 60 nature Cured at 120°C for 1 hour Old 5° Solubility 25.9 44.2 37.6 44.3 Shore “A” Hardness 86,8 90,8 89.8 93.512 The average surface in the fracture is number 10.250 36,000 70,000 27,0 00 Moderate number of bends until breakage 8.000 20,000 60,000 25, 000100℃ 455 495 460 440100% Mosoulation Room temperature 1357 1314 1292 1223 100°CL12g 11 45 1055 1025100°C240615701?80 124610 0℃ 537 398 560 263 Crescent Tear Room temperature 489 510 470 478100°C371418354 352 stress relief Elasticity E (PsI) 7810 9500 8600 - 1j - 4E'M O,0276,0,03410,0392--Is it in Table 1? Now, B’s raw h’ ・・・When compared with that of the control example, the product has excellent resistance to cut growth. :Ter, us Shows excellent improvement in Flex. Product B is molecular needle 200 A po IJT HF polymer with a MO terminal of 0 is used.

The equipment and method used to perform the non-Teτus Flex test was RubberC Hemistry and 1'technology, Volume 38, April, 730-7 40 pages, November 1965.

Example I Implemented by using a large proportion of TIiF at the O terminal of the polymer The method of Example I was repeated. The proportions, conditions, and test results are shown in Table ①.

(NH2+0B)liVcO ratio -1,025BHNE2/IVCO ratio 1.0 25 7vCO terminal Molecule f71320 100 10o 100 (NGO6,4%) Molecular weight 2000 15- (UH number 58.7) Molecular weight 5000 20.6 (Number of OBs: 21.6) 4 Dispersion of NaCl 3MIJA 34.3 38.2 4 Z6 DOJ) 6 6 7.5 nature M, glfMl, Vr, 0.050 0.031 0.041 Bath disintegration 2 5.9 49.6 43.8Share"A"Hardness 86,8 90,5 89 ．． 0 cut growth The average surface until rupture is number 10.250 53,500 43,700 until rupture Medium bending number 8.000 60,000-100”C455415475 Table ■FJ1 100 temperature room temperature 1357 1218 1119 100℃ 11 28 1033 910 Torn ■] Nei Tensile Room Temperature 4919 34.44 24 91100°G 2406 1654 1033 Elongation at break Room temperature 498 514 440100°C537540201 crescent Tear Room temperature 489 458 399 100℃ 37i 371 171 stress relief Elasticity E (PSI) 7810 Viscoelastic M O, 0276-1 Example W low (tvB2+OH)/AIC(J The method of Example 1 was modified by using the ratio ir@;Iz. allocation, conditions and The test results are shown in Section M.

Koma rt1 table (N)12 +C1/7) /△′C゛0 ratio -0,9750,975IVJi 2/IV (J, '0 ratio o9758 I CO; l; Molecule jQ l 320 100 100 100 (8・C゛(]66.4.% Molecular width 2000 10 (0 number 587) Molecular weight 5000 9.2 (UJi number 216) nature 1 hour at 120°G - H1 sulfidation Common understanding 1st life 20.1 37.0 33.8 cut growth 16% boar shape, until breakage The cycle of 4400 5700 4700 times The average white in 161i is a number + 4.500 40.000 17.250&a yr-1 ((Q medium bending number 12.000 30.000) 7.0005e i) Mosolation; Low deformation Room temperature 580 530 500 100°G 450 470 422 100% modulation Frost 1840 1281 1278 100℃ 1062 1040 104 8 breakage discount! Former tree room (easy/i 4646 4653 3955100°G 221 = 1 2084 1637 Broken vinyl ■ Temperature room temperature 403 532 454100°C483570353 crescent Tear Room temperature 530 48.5 481 This inn BK is also like in Example ■ , using 110 terminal poly(+)TEF' weight/f5-terrestrial acid lO parts with a molecular weight of 2000. The product F had better resistance to cut growth and Texu compared to the control V' product. s Flex has been improved.

Example■ icI; If O end of molecular body, ) q +) f il F 2 stone ratio −〇ha 1 That there is (・This is the one for actual sister measurement 1?・, 2: Return 7. Cave”, Article 2 1: and test development meeting Table ①.

(Nli2+UjJ)/hcO ratio -0,9750,', "J75 0.9 75! Vji2/NCO ratio 0.975 c'c o terminal (,/VCCJ6.4%) 100], 00 100 1001jO terminal Poly Tli F lj meeting Body weight 2000 (Olichi,';;58.7) l 5.7 22-4 - Molecular weight 5000 (O1i number 21.6) 20.7 J) UP　6　7.17.6　'7.5 Sex value At 120℃] Interleaf hardening Table ■Continued @Distribution 20.1 33.7 42!5 31.2Share “A”7 flights 1i 9 2. o 91.5 90.5 90.0 Cut growth 16% all 2 forms, broken v■ Cycles at 4,400, 8,000, 8,700, 9,900 yen bending at break l Ei 14,500 55,000 57,500 21,500 Medium at break 1 Bending v, 12,000 45,000 45,000 --51 ≠ Modulation Yon Low deformation Room temperature 580 515 510 490 100°C 450 470 465 425 100% modulation Room temperature 1840 1256 1329 115510θ°C106210901 003950 Tensile against fracture Room temperature 4646 4113 4228 34791 00°C 2214209715131252 Tension Room temperature 403 4 91　560　480100°C483590453283 Part ■Second blow (crescent) Tear Room temperature 530 429 459 423 IiO end with molecular weight 2000 Generation using Po +) TBF! thIB and I have improved cuts compared to controls It showed resistance to growth and Tezus Flew.

Example■ Comparing high molecular weight poly I'BF with similar weight and active hydrogen and incyane-1. By adding free incyanate and using it in a high proportion, the results of Example ■ The method was revealed. Instead of dioctyl phthalate, commercially available product () “1etoL 4- GO, using polyethylene glycol di(2-ethyl hexoa) . The proportions, conditions and test results are shown in Table 7.

(7Lljj2 Shishiri i) /A'tZ'U ratio -1,0251,0251ji No’y/1νCO ratio 1.025 Table V continued IVC “0 end Molecular weight 1320 100 100 100 (A' C06, 4%) HO terminal PolyTHF polymer Molecular weight 2000 (OH number 58.7) -10- Molecular weight 5000 (Number of OBs 216) -10 Caytwr-2134, 2732133, 3FleZ-4GO66, 66-6 nature Cured at 120℃ for 1 hour DMF/Tl1F.

25/75ch Solubility 31.7 47.0 33.3S hole″+A″ Hardness 9Z0 9 Z0 9Z8 cut growth 16% deformation, up to breakage Cycle 45 mountains, 0 5200 460G2 Tetus Flez* The average surface up to breakage is number 24,50θ 51,000 20. (up to 10 breaks) Medium songs are number 12,000 35,000 i8,0005tlo module Yon, Low deformation Room temperature 570 445 475 100℃ 460 445 440 100% modulation E7 Room temperature 1397 1207 1206100°Clθ49 961 94 6 Tensile strength at break Room temperature 4542 3809 3863 100℃ 2245 19 44 1840 Elongation at break Room temperature 482 507 490 100℃ 529 553 507 Crescent (crescent’) Tear Room temperature 489 453 444ioo°C223382350 In this case as well, the product (J) containing Po I) TEF with a molecular weight of 2000 is All had improved cut growth resistance and Texu, s Flew. .

Example■ High molecular weight poly(po+)TliF whose molecular weight gradually increases and active hydrogen and incyanate By using comparable ratios, it is possible to conduct experiments without adding free incyanate. The method of Example ■ was repeated. The ratio, conditions and test results are shown in Table ①.

In this case as well, the product containing Sool with a molecular weight of 2000 was It was excellent in terms of resistance to eye growth and Tezus Flex.

Example■ f(, that Trimethylene dalycol and hexamethylene glycol each having approximately the same molecular weight The method of Example 1 was repeated several times by using equivalent amounts of polyether made from I - but similar improvements were obtained.

Example ■il Instead of complexes, respectively (a) NaCl ・3 (4,4'-diaminosophenyl) (b) NaCl ・3 (oxydaniline) (c) NaCL ・3 (4,4'-diamiline) By using an equivalent amount of a complex comprising (3-3,3-propane) The method of Example (1) was repeated several times, and similar improvements were obtained.

Polytetrahydrofuran is a polyether polyinsyanate brepolymer. In addition, polyetherduol is suitable as a polyether, but It is also suitable to use other ethers, preferably glycols having 2 to 6 carbon atoms. be.

Furthermore, instead of the preferred complexes of polyamines, polyamines may be used in uncomplexed form. In both cases, a suitable vortex is used, and in this case, the elastic body is fixed, that is, hardened, at a low temperature. other Typical polyamine curing agents are listed above.

Some features of the present invention will be described in detail in 1-1 with regard to various specific examples thereof. However, it is obvious that other modifications may be made within the spirit and scope of the invention. There is no intention to limit the invention to the precise details set forth above except as provided in the claims below. It's not what I intend.

international search report

Claims (1)

[Claims] 1a, contains a glycol having 2 to 6 carbon atoms, and further has a plurality of terminal -NGO groups, and A preformed isoether polyester having a number average molecular weight of approximately 800 to 2,500. Socyanate 85-95 parts by weight; b, number average molecular weight approximately 1000-3 (10o 5 to 15 parts by weight of diol containing The pre-generated 1. Weighing of the polyether polyisocyanate and the Sool 100 copies in total; 1. hand The equivalent ratio of active hydrogen in the C9 curing agent per incyanate group is 09 to 1.2. polyamine curing agent in proportions such that When curing the composition, alb and C react simultaneously, against the growth of cuts. Polyether polyurethane with improved resistance to cracking and cracking over time Composition. 2 The ratio is 12 to 12% polyether polyisocyanide 8% to 92% 82. The composition of claim 81, wherein the composition is in the amount of 8 to 13N. 3 Shade drying +-, +Priether polyisocyanate is poly(teto seed) 3. The composition of claim 2, wherein the composition is coated with Ronra/) noinonoanate. Ia, 9; tζ riethersool is poly(tetrahydrofura/)diol A composition according to claim 3. 5 The polyether polyisocyanate produced in the shade is 1000 to 3000 5. The composition of claim 4 having a number average molecular weight. 6. Claim 5 wherein the polyether sole has a number average molecular weight of about 2000. The composition described in. 7. Claim 5, wherein the polyamine curing agent is in the form of an alkali metal halide complex. Compositions as described. 8. The composition according to claim 7, wherein the alkali metal halide is NaCl. 9. The NaC'l complex has 3 molecules of duamine per molecule of Na, C. The composition according to claim 8. 10 The complex has 3 molecules of methylene dianiline per 1 molecule of NaC. The composition according to claim 9. 11. The composition according to claim 10, wherein the complex is dispersed in so-octyl phthalate. thing. 12 Polyether polyinsyanate is aromatic with 1 mol of polyether diol Claim 3.4.5.6.7. which is a reaction product of 2 moles of group diisocyanate. 8.9.10 or 11. The composition according to any one of 8.9.10 and 11. 1371′? Reether polyisocyanate is polytetrahydrofuran diol Claim 3. The reaction product is 2 moles of citoluene soisosoauto per mole. 4.5.6.7.8.9, IOnu is the composition according to any one of 11. 14. Claims: A composition obtained by heating the composition according to 2 to a temperature of at least 100°C. .