JPS5840316A - High molecular modified polyol, production and manufacture of polyurethane product - 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 The present invention relates to polymer-modified polyols useful in polyurethane production.

Stable dispersions of polyurethanes in high molecular weight dihydric alcohols having essentially exclusively secondary hydroxyl groups are known from GB 1,053,131. This dispersion is a polymer-modified polyol and is produced by reacting an organic diisocyanate and a glycol in a high molecular weight dihydric alcohol. This dispersion is also designed for use as a base glue and is particularly useful as a base glue when compatible with textiles and dyes.

EP 0 032 380 describes the use of storage-stable suspensions of hard crystalline organic components in soft polyols with a functionality of 2 to 8 and a hydroxyl number of 150 to 700. . This crystalline component can be a polyurethane obtained by reacting an organic diisocyanate and an aliphatic diol. This suspension is used to produce rigid foams.

According to one embodiment of the invention, at least 1000
a polyisocyanate in the first polyol having a molecular weight of greater than 2, preferably about 3, an average functionality (i.e. an average number of isocyanate-reactive hydroxyl groups in each molecule) and a hydroxyl number of less than 150; , (a
or (b) a dispersion of the reaction product with a second polyol which is not polyethylene glycol but is a polyol having a molecular weight of less than 250 and containing no nitrogen atoms. A polymer-modified polyol consisting of the following is obtained.

Other embodiments of the invention include methods of producing polyurethane products, particularly polymer-modified polyols used in the production of flexible polyurethane foams, and the polyurethane products thus obtained.

The term "polymer-modified polyol 1" additionally means all polyols containing all polymeric materials.

This term is clear to those skilled in the art and includes, for example, polyisocyanates, primary amines and secondary amines.
Dispersions of polyureas and polyhydrazo-dicarbonamides in polyethers obtained by reacting with hydrazine or hydrazides in whole polyethers are used in GB 1,453,258, which describes the entire dispersion of polyureas and polyhydrazo-dicarbonamides in polyethers.

The first polyol used in the invention can be any polyol used in the production of polyurethanes or a mixture thereof, in which case the polyol is 1. molecular weight of at least 1000, average functionality greater than 2 and 1
Has a hydroxyl number of less than 50. This polyol is of the type used in the manufacture of flexible foams;
It is well known to the polyurethane engineer and demonstrated in the relevant publications. Usually the polyol is a polyether polyol, but it could easily be another type of polyol such as a polyester polyol. Of particular importance are 1000-10000, preferably 10
Polyether polyols with a molecular weight of 00 to 8,000, especially polyether triols with a molecular weight of 2,000 to 6,000. Preference is given to polyoxyalkylene polyols which are obtained by reacting alkylene oxides or mixtures of alkylene oxides with active hydrogen-containing initiators. Ethylene oxide terminated polyoxypropylene polyols are particularly useful in the production of high modulus flexible polyurethane foams.

Other poly(oxypropylene-oxyethylene) polyols in the form of random or block copolymers are also useful.

Suitable organic polyisocyanates, i.e. organic incyanates having two or more incyanate groups, are used in the present invention, including aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates. be able to. Such isocyanates are well known to the polyurethane engineer and are demonstrated in relevant publications (see, for example, GB 1,453,258).

Of particular importance are aromatic polyisocyanates, such as tolylene diisocyanate (TI) 1) and diphenylmethane diisocyanate CMDI), which are commercially available in substantially pure and crude form. In particular, the aromatic polyisocyanates include 2,4- and 2,6-)lylene diisocyanates and mixtures thereof; diphenylmethane-2,4'- and -4,=1'-diisocyanates and mixtures thereof (generally pure MDI), for example 70 to 100% by weight, especially 80% by weight of 4,4'-isomers and 2,1'-S" tetramers 30
polyphenylbolimethane polyisocyanate prepared by phosgenation of a mixture of polyamines obtained by condensing a mixture of nearaniline with formaldehyde containing up to 20% by weight, in particular 20% by weight;
Ml) mixture with I (generally crude or polymeric Ml') T
); and pure or crude, TI)I, and AI
Mixtures with D I, such as TDI'60 weight and M
Includes mixtures containing a DI40 weight ratio. In order to introduce an effective incyanurate, calzediimide, uretonimine, buiret or allophanate content, it is also possible to use diisocyanates modified in known manner.

Other polyisocyanates that can be used are isocyanate-terminated prepolymers, such as diisocyanates and one or more low molecular weight polyisocyanates, such as trimethylolpropylene, cyclopylene glycol or tripropylene. contains the reaction product with the insufficient amount of ole.

The second polyol used in the invention can be a polyethylene glycol having a molecular weight up to 600, including diethylene or triethylene glycol.

However, this polyol is 200 to 6001, especially 20
It is advantageous to have a molecular weight of 0 to 300.

Furthermore, the second polyol may be a polyol having a molecular weight of less than 250 and containing no nitrogen atom instead of polyethylene glycol. It can be selected from various nitrogen-free compounds having two or more hydroxyl groups. This polyol preferably has 12 primary hydroxyl groups, but all other hydroxyl groups can be present in the secondary or secondary form. Suitable compounds that can be selected are diols, such as mono-alkylene glycols, such as evapoethylene glycol, 1,2-propylene glycol, especially 1.3-10
Pyrene glycol, 1,4-butylene glycol and H1
．． Includes 6-hexylene glycol as well as triols such as glycerol and trimethylol.

According to another embodiment of the invention, the polyisocyanate is prepared in the presence of a first polyol having a molecular weight of at least 1000, an average functionality of more than 2 and a hydroxyl number of less than 150. or (b) a second polyol which is not polyethylene glycol but has a molecular weight of less than 250 and does not contain nitrogen atoms. is obtained.

When carrying out the process of the invention, the polyisocyanate and the second polyol are mixed in a ratio of about 0.5:1.0 to 15:1, preferably 0.8:1.0 to 1.1:1.0, especially 10:1
．． Mix together in the presence of the first polyol in a molar ratio of 0. The molecular weight and viscosity of the polyaddition product thus produced can be varied by adjusting the proportion of polyisocyanate and second polyol. 1.0:
Molar ratios greater than 1.0 are generally considered useful with a second polyol having three or more hydroxyl groups rather than with a diol.

The molecular weight of the polyaddition product can be varied by charging a monofunctionally reactive compound that acts as a chain terminator. Such compounds include monofunctional incyanates and -hydric alcohols. This compound can advantageously be used in amounts up to 257 times the second polyol.

The reaction may be catalyzed by a catalyst of the type, for example organometallic compounds such as stannous octoate and dibutyltin dilaurate or amines such as triethylenediamine, in the amounts normally used for the production of polyurethanes. can.

The concentration of polyaddition products in polymeric modified polyols can vary within wide ranges, but for most purposes,
It is 1 to 80% based on the total weight of the polymer modified polyol.
% by weight, usually between tO and 60%, typically 20% by weight. High concentration of polymer-modified polyol, i.e. 50~
It may prove advantageous to produce 60 inches and dilute this to 10 to 20 inches with an excess of the first polyol before use. This reaction is exothermic, and generally the higher the concentration of polyaddition product to be formed, the more exothermic the reaction.

It has been recognized that in the case of some polymerically modified polyols according to the present invention, the polyaddition product cannot be produced solely from the second polyol, but can incorporate units derived from the first polyol. It will be done. but,
In many cases such units are formed in only a small proportion of the total units in the polyaddition product and the components are commonly selected to achieve this condition, e.g. The relative reactivity of the hydroxyls of the polyol is selected.

The polymer-modified polyol according to the invention is produced by dissolving or dispersing a second polyol or polyisocyanate in a first polyol and subsequently adding the other of said second polyol or polyisocyanate to this solution or dispersion under stirring. It can be produced by the Nototsuchi method by adding This dispersion is suitable for efficient mixing of reactants.
Usually has a fine particle size. The viscosity of the product also tends to be low. Furthermore, polymer-modified polyols can also be produced continuously by in-line blending. For this method, the polyisocyanate and the two polyols can be pumped at a controlled rate and mixed simultaneously, or the second polyol or polyisocyanate can be mixed with the first polyol; Subsequently, the other of the second polyols or polyisocyanates mentioned above can be added and mixed.

It is usually sufficient to add the ingredients at room temperature, but if necessary the exothermic reaction and the heat generated by the high-q shear mixing will raise the temperature to 150°C.

The selection of components for the polymer modified polyol is governed by the need to produce a dispersion rather than a solution. As a criterion, it is advantageous for the second polyol to have a high solubility in the incyanate with which it reacts and a low solubility in the first polyol. It is advantageous for this first polyol to have a high molecular weight (□) rather than a low molecular weight. It is also desirable to maintain the relative activities of the first and second polyols with respect to the polyisocyanate as large a difference as possible.

The polymerically modified polyols according to the invention are useful in the production of polyurethane products, especially polyurethane foams.

Polyurethane products are obtained by reacting polyisocyanates with polyols. The polymerically modified polyols according to the invention can be used as polyol components, in particular for producing flexible polyurethane foam products. The properties of this foam depend on the particular polyol selected as the first polyol in which the polyaddition product is dispersed, as well as the polyisocyanates and other ingredients commonly used in the production of polyurethane foams. The other components can be selected in a known manner to produce the desired foam mold.

Polyisocyanates that can be used for the production of polyurethane products are comprehensively described in that publication and include the organic polyisocyanates mentioned above for the production of polymer-modified polyols. The particular polyisocyanate used can be the same as used to make the polymer-modified polyol or can be different.

The polymer-modified polyols according to the invention are particularly useful in the production of highly modulus flexible foams for cushioning materials and similar applications. This type of foam and its method of manufacture are well known in the polyurethane foam industry. Such foams made from polymer-modified polyols according to the invention have the advantage of increased hardness and shrinkage.

For foams of this type, the polymerically modified polyols are preferably prepared from polyoxyalkylene polyols, in particular ethylene oxide terminated polyoxypropylene polyols, and are polyincyanates which can be used for the production of polymerically modified polyols. TD I, pure, crude or modified M J31 as described above, or with a mixture of TDT or TDI prepolymer and pure or crude MDI.

The highly preshockable polyol according to the invention can be used directly, either by being produced or by being stored. If this polymer-modified polyol is produced continuously by in-line blending, the intermediate storage vessel between the individual blending device and the polyurethane mixing head is
It can optionally be used to complete the reaction of the polyisocyanate with the second polyol, in which case the reaction is slow.

The polymer-modified polyol dispersion has good storage stability and can be stored before use.

Other conventional ingredients can be used in the production of polyurethanes. The components include catalysts such as tertiary amines and organotin compounds, surfactants, crosslinkers or chain length regulators such as low molecular weight diols, triols and diamines, flame retardants such as halogenated alkyl phosphates, fillers. and pigments. The blowing agents used in the production of polyurethane foam include water, which is reacted with the polyinocyanate to form carbon dioxide, and inert, low-boiling liquids such as halogenated hydrocarbons, such as citrichlorofluoromethane and Includes dichlorodifluoromethane. Cell stabilizers, such as polysiloxane-polyalkylene oxide block copolymers, can be used to stabilize or control cells in the □ form.

The minor components and blowing agent 41 used depend on the nature of the product required and can vary within ranges well known to those skilled in the art of polyurethane foam. In the case of water-foamed flexible foams of high modulus, it is suitable to use 10 to 5.5% by weight, preferably 15 to 40% by weight, of water, based on the weight of the total polyol component. Inert, low-boiling liquids can additionally be used as blowing agents if this is desired to reduce foam density.

Generally, the composition of the foam-generating reaction mixture has a ratio of incyanate groups to active hydrogen atoms of 07:1 to 1.2.
:1, preferably from 08:1 to 1:1.

The one-shot, prepolymer or quasi-prepolymer method is
It can be used if it is suitable for producing special molds of polyurethane.

The components of the polyurethane-forming reaction mixture can be prepared in any conventional manner by:
They can be mixed together, for example, by using all the mixing devices described in the literature for this purpose. If desired, some of the individual components can be preblended to reduce the number of component streams needed to bring together the final mixing process. It is often advantageous to have two flow systems, in which case one stream consists of polyinsyanate or prepolymer;
The second stream consists of all other components of the reaction mixture.

The present invention will be explained in more detail by the following example, in which all turtles" and 1" are 1" unless otherwise specified.
Parts by weight (or % by weight).

Examples 1 to 6 90 parts of oxypropylated chrycerol having a molecular weight of 3000 was added to tolylene diene sulfate (8 (1:2°2:4/
2:6 isomer) 655 parts and 0 dibutyltin nolaurate
．． Blend with 03 parts. Immediately after that, glycerol 3
45 parts are added under vigorous stirring.

An opaque dispersion forms. Similar results can be obtained by replacing glycerol with the following polyol and adjusting the amount of tolylene diisocyanate to maintain a total weight of the two components in molar ratios of 1 and 10 parts.

1 Nidosujigo 2 Ethylene glycol 3 Diethylene glycol 1 Triethylene glycol 5 1
, =1~Butanediol 61.2-Propylene glycol (opacity formed on standing).

''Usually the same result as in Example 1 was obtained by keeping the same total weight and increasing the molar ratio of glycerol to tolylene diisocyanate to 1.
．． This is obtained when the ratio is changed to 0:1.5.

The results are essentially the same as in Example 5, keeping the same total weight.
It is obtained when the molar ratio of 4-butanediol and trirefedisocyanate is changed to 1.0:0.66.

Examples 1-8 are repeated substituting an equivalent amount of 4000 molecular weight polypropylene glycol for the 3000 molecular weight oxyzolobylated glycerol, yielding essentially the same results.

For comparative reference, replacing the oxypropylated glycerol of Examples 1-8 with a 6000 molecular weight material with 16% ethylene oxide end groups results in a solution rather than a dispersion.

16 thiethylene oxide end groups, molecular weight 6000
Oxypropylated glycerol (OPO) is mixed with polyethylene glycol (P F,G ) under vigorous stirring. Pure MDJ modified with uretonimine is optionally mixed with 1,4-diazabicycloC222''J octane (D
ABOO) catalyst in the presence of about 5 minutes and stirring continued for a further 5 minutes.

The molecular weights of the polyethylene glycols and polyethylene glycols used are listed in Table 1.

OI'G 65.0 65.0
65. OPIUG (molecular weight 200) 20.3
- +-P B G (molecular weight 300)
23.6 -PEG (molecular weight 60
0) --28,2DAr3COO,1'-Ml) T 14.7 1111
6.8 In each of these examples, glycol 1 el (14,
MDIo, present for reaction with 5 mol. Therefore,
Sufficient isocyanate groups are present for reaction with 50% hydroxyl groups in polyethylene glycol. The reaction is carried out at a concentration of 35% by weight of polyaddition product, based on the total reaction mixture.

Next, for comparison, PE() of Example 17 (molecular weight 200)
Replacing PEG (character weight 1000) and polypropylene glycol (molecular weight 425) does not result in a satisfactory dispersion. In the former case, some particles are produced under static conditions, but the product is semi-solid. In the case of ridges, the product is mostly gel-like.

The polymer-modified polyol was prepared using the methods of Examples 17 to 19.
EG (molecular weight 200) and PEG (molecular weight 30
0) but with different concentrations and reaction rates (.

That is, the ratio of isocyanate groups to hydroxyl groups in PEG is different). The concentration of the dispersion obtained in the polymer-modified polyol depends on the number of hydroxyl groups actually present in the PE ( The reaction rates, expressed as a percentage of the number of groups, are shown in Table 2.

Highly elastic polyurethane foams were made from polymer-modified polyols. The properties of these foams are compared in Table 2.

In Examples 22 and 23, respectively, the results shown show that during production two forms (one made from a polymeric modified polyol dispersion produced at a concentration of 50%, the other
One is an average of remarkably similar results (within experimental error) obtained from the same polymer-modified polyol dispersion, but diluted to 20% with OP.

■≦shiL Example rooftop Yu^ Uni used l' EO (D molecular weight 200 300
300 300 Reaction rate (%) 80 80. 8
0 1.00 pressure 9) Permanent set (%) 9
7 10 10 Tensile strength CkN/lt? )
125 105 105 115 Elongation at break (%)
160 150 145 155 Tear strength (N/m) 350 340 330 345 Lens 55 56 58 59 Indentation hardness 136 116 114 122 (N/m)
Indenter with diameter 200rrLtrL) Core density (kg/M
3) 42 44 42 42 (GB)■8
209218 0 Inventor Raymond Joseph Murkrow Hexabone House, Blackley, Manchester, UK (no street address)

Claims (1)

[Scope of Claims] 1. In the polymer-modified polyol, at least 10
a polyisocyanate in a first polyol having a molecular weight of 0.00, an average functionality greater than 2 and a hydroxyl number less than 150; , characterized in that it consists of a dispersion of a reaction product with a second polyol, which is a polyol having a molecular weight of less than 250 and containing no nitrogen atoms,
Polymer modified polyol. 2. In a method for producing a polymer-modified polyol, a polyisocyanate having a molecular weight of at least 1000, an average functionality of greater than 2, and a hydroxyl number of less than 150 is added to or (b)
) A method for producing a polymer-modified polyol, characterized in that it is reacted with a second polyol which is not polyethylene glycol but is a polyol having a molecular weight of less than 250 and containing no nitrogen atoms. 3. A process for producing a polyurethane product by reaction of a polyisocyanate and a polyol, in which the polyisocyanate and the polyol in a first polyol have a molecular weight of at least 10,000, an average functionality of more than 2 and a hydroxyl number of less than 150. , (a) is a polyethylene glycol having a molecular weight of up to 600, or (b) is not a polyethylene glycol and is a polyol having a molecular weight of less than 250 and containing no nitrogen atoms. 1. A process for producing polyurethane products, characterized in that a polymer-modified polyol is used as a dispersion.