JPS6253371A - Asphalt-containing polyurethane and production thereof - Google Patents

Abstract

PURPOSE:To obtain a composition free from odor, stickiness and staining property and giving a foam containing petroleum pitch in high affinity and bindability, by dispersing petroleum pitch uniformly in a polyurethane. CONSTITUTION:The objective composition can be produced by dispersing petroleum pitch uniformly in a polyurethane. Concretely, petroleum pitch is dispersed in the form of fine particles in one or more components of polyurethane raw materials selected from a polyisocyanate component composed mainly of polyisocyanate, a polyol component composed mainly of a polyol and a plasticizer component composed mainly of a plasticizer, and the polyurethane raw materials are made to react with each other under stirring to effect the uniform dispersion of the petroleum pitch in the polyurethane. The petroleum pitch used in the above process has a softening point of 130-250 deg.C and a fixed carbon content of 40-80wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bitumen-containing polyurethane that can be applied to all polyurethane foams such as flexible, semi-rigid, and rigid polyurethanes, as well as other polyurethanes, and a method for producing the same.

It is known to incorporate f' into the polyurethanes of polyurethane foams.

Tar polyurethane uses tar as bituminous material, and has been used in practical use because tar has good compatibility with polyol and polyincyanate, which are raw materials for polyurethane. However, because of the residual tar odor and the fact that tar contains carcinogenic substances, the use of asphalt in place of tar is being considered. However, unlike tar, asphalt does not have good compatibility with common polyurethane raw materials, so there are various practical problems. Therefore, instead of mixing asphalt with polyurethane raw materials and foaming them, polyurethane foam was impregnated with an asphalt solution in which asphalt was dissolved in a volatile solvent, or an asphalt emulsion in which asphalt was emulsified in water, and then dried. . However, the solvent
There is a risk of catching fire while working, there is a problem with pollution, and emulsions require a long time to dry. have. There was a problem with the product being sticky when handling it.

On the other hand, Japanese Patent Publication No. 60-28298 proposes a new method for producing bituminous foam.

This method consists of a polyol, a polyincyanate blowing agent,
For the total production of bituminous foam by mixing and reacting the raw materials of fillers, catalysts and other auxiliaries, (a) a bituminous material (asphalt) which is solid or semi-solid at room temperature; 150 to 200 parts by weight per 100 parts by weight, part) used as a blowing agent with an inorganic hydrate with a decomposition temperature of 75° to 300°C, and (C) mixing temperature of various raw materials at the time of foaming to 90°C.
Polyurethane foam is produced by foaming at a high temperature of ~250°C. However, this method uses a bituminous substance that is solid or semi-solid at room temperature (not liquid), and uses a material that is compatible with asphalt as the polyol, such as diene polyol (polybutadiene polyol), castor oil polyol, etc. , specific polyols such as dimer acid polyols are mainly used. Also, the mixing foaming temperature is 90~
There are problems such as the high temperature of 250°C being required and the use of a specific blowing agent.

In particular, there is a demand for polyurethane foams that can be foamed at room temperature and that can be foamed by injection molding, and the method described above is suitable for such foams.

The present invention satisfies these two needs by using petroleum pitch as a bituminous material and making it possible to mix bitumen with polyurethane for various polyurethane products, including polyurethane foam. The object of the present invention is to provide a polyurethane that contains bitumen and has no problems with odor, stickiness, or staining, and has an affinity for bitumen, and a method for producing the same.

The present invention provides a bituminous polyurethane which is characterized by uniformly dispersing petroleum pitch in the polyurethane, and a polyisocyanate component whose main component is polyincyanate, and a polyisocyanate component whose main component is polyol among the polyurethane raw materials. Petroleum pitch is dispersed in the form of fine particles in one or more of the polyol component or plasticizer component whose main component is a plasticizer, and the polyurethane raw materials are mixed and reacted to form petroleum pitch in the polyurethane. The gist of the present invention is a method for producing dipolyurethane containing bitumen, which is characterized by dispersing the bitumen in a uniform manner.

The petroleum pitch used in the present invention is a petroleum pinch produced by a process of high-temperature heat treatment of crude oil vacuum residue oil, and has a high softening point (ring and ball method) of 130 to 250 °C and a fixed carbon content of 40 °C. It is as high as ~80% by weight. It is also more aromatic than asphalt, and has aromatic properties similar to coal tar pinch. Petroleum pitch powder is porous and hydrophobic, but it has poor wettability and affinity for polyisocyanates, polyols, etc., which are the raw materials for polyurethane. In good condition.

Other bituminous materials and heavy oils can be used in conjunction with petroleum pitch. Examples include tar pitch, asphalt, aromatic or naphthenic heavy oils, process oils, and tar-based high boiling point oils. When these are used together, they should be used in an amount equal to or less than the amount of petroleum pitch, preferably 50 gw downwind of the petroleum pitch. For example, about 20% by weight of process oil may be added to and mixed with fine powder of petroleum pitch to moisten the petroleum pitch and granulate it before use.

This makes it easy to disperse the petroleum pitch when it is added to and mixed with the polyurethane raw material.

The polyisocyanate component mainly composed of polyisocyanate as used in the present invention refers to a component containing polyisocyanate, which is one of the raw materials for producing polyurethane foam and other polyurethanes by reacting with polyisocyanate and polyol. In addition to the case of using only polyisocyanate, it may contain plasticizers, fillers, catalysts, crosslinking agents, blowing agents, and others other than polyisocyanate.

The polyol component containing polyol as a main component in the present invention refers to a component containing polyol, which is one of the raw materials for producing polyurethane foam and other polyurethanes by reacting with polyisocyanate-1-(5 polyol). In addition to polyol alone, it may contain plasticizers, fillers, catalysts, crosslinking agents, blowing agents, and other substances in addition to polyol.

As the above-mentioned polyincyanate and polyol, conventionally known ones are used. For example, as polyisocyanates, tolylene diisocyanate (TDI), diphenylmethane diyn 7anate (MDI), crude MDI
, hexamethylene diinodine (HMDI),
Xylylene diisocyanate (XDI), hydrogenated TD
I, hydrogenated MDI, metaxylylene diisocyanate, polymethylene polyphenylisocyanate (PAPI
)and so on. It is also possible to use prepolymers containing terminal isocyanate groups obtained by reacting these polyisocyanates with polyols.

Polyols have two or more hydroxyl groups in their molecules, and include polyester polyols, polyether polyols, polymer polyols, and others. Polyester polyols include dicarboxylic acids such as adipic acid, phthalic acid, dimerized sulfuric acid, and maleic acid, and ethylene,
Glycols such as propylene, butylene, diethylene,
These include polyols obtained by complete reaction with diols, triols, and polyols such as glycerin, trimethylolpronochloride, and pentaerythritol, and castor oil.

Polyether polyols include propylene glycol, glycerin, trimethylolpropane, other polyols and polyamines, and propylene oxide (PO).
, ethylene oxide (EO), butylene oxide,
There are polyols to which methyltrimethylene oxide, dimethyltrimethylene oxide, etc. have been added. Examples of polymer polyols include polyols having two or more hydroxyl groups at the end of the molecule or within the molecule, such as polybutadiene, styrene-butadiene copolymer, and butadiene-acrylonitrile copolymer. Other examples include polyols of linear polymeric esters of ethylene glycol and terephthalic acid, and acrylic polyols of acrylic acid derivatives.

The plasticizer used in the present invention is used as a plasticizer or additive for polyurethane, and includes diethylhexyl phthalate, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, other known plasticizers, and aromatic or naphthenic plasticizers. Process oil is used. Most polyurethane products do not use plasticizers, but plasticizers may be used when fillers are added.

Other materials used as the polyurethane raw material, such as fillers, catalysts, blowing agents, crosslinking agents, dispersants, auxiliaries, and others, are conventionally known materials.

When producing the bituminized polyurethane of the present invention, the petroleum pitch can be introduced into the polyurethane during the process in which the polyurethane raw materials are mixed and reacted to produce the entire polyurethane, or before the polyurethane raw materials react.
A method is adopted in which the entire required amount of petroleum pitch is mixed into the polyurethane raw material while it is miscible at least in the initial reaction.

Specifically, (1) petroleum pitch is pre-mixed with either the polyisocyanate component or polyol component of the polyurethane raw material, or with a plasticizer that is added to these components or a mixture of these components as necessary. (2) polyinsyanate component of polyurethane raw material,
There is a method of adding and mixing petroleum pitch when mixing the polyol components or to the mixed mixture.

In particular, the +11 method involves adding and mixing petroleum pitch powder to, for example, a polyol component or a part thereof, or a plasticizer, and thoroughly pulverizing this through an attritor, mill, etc.
By dispersing it in the form of fine particles, it can be dispersed in diol components and plasticizers. In the petroleum pitch dispersion thus obtained, the petroleum pitch particles are smoothly and uniformly dispersed, and no sedimentation is observed.

This appears to be due to the fact that polyols and the like permeate and are adsorbed into the porous structure of the petroleum pitch fine particles. When mixed with polyols, polyisocyanates, etc., it has good mixing and dispersion, and petroleum pitch improves mixing. -! In addition, petroleum pitch is evenly dispersed and integrated into the polyurethane structure produced by the reaction. It is also possible to disperse petroleum pinch into the polyisocyanate component, but the grinding process generates a small amount of heat and promotes the reaction of the polyisocyanate with moisture, so replacing the air with dry air or a non-humid nitrogen stream is recommended. It is necessary to perform a crushing process. Therefore, when performing the grinding process, it is preferable to mix petroleum pitch with polyol, plasticizer, etc. Most preferably, the petroleum pitch is dispersed in a milling process;
It can also be mixed and dispersed in polyols, plasticizers, etc.

In this case, in order to speed up the mixing and dispersion, it is also good to add a plasticizer, polyol, etc. to the fine powder of petroleum pitch, wet it, and form it into granules.

′! t. When mixing the polyisocyanate component and the polyol component using the method (2), or when mixing petroleum pitch into the mixture, partially apply the method in +11 to improve the mixing and dispersion. In addition to this method, it is also possible to wet fine petroleum pitch powder with a plasticizer, polyol, etc. and make it into granules.

In the method (1), when the petroleum pitch is pulverized and mixed using a grinder, it becomes dispersed in fine particles and therefore becomes viscous. It depends on the type of petroleum pitch, polyol, plasticizer, etc., but the concentration of petroleum pitch is limited to 65% by weight (the remainder being 35% by weight of polyol, plasticizer, etc.), and in order to make it into a paste or liquid form at room temperature, Usually petroleum pitch is (
b) It is carried out at a ratio of heavy weight or less.

The ratio of petroleum pitch to bituminized polyurethane is 150 parts by weight or less, usually 100 parts by weight or less, per 100 parts by weight of polyol.

Known methods are used to produce polyurethane foam and other polyurethanes, and the above (+1, (2)
Z5, petroleum pitch can be incorporated into polyurethane in a method such as Z5.

The bituminous type 9 polyurethane of the present invention can be applied to soft slab foam, soft foam molded products, hard foam injection molded products, hard foam spray molded products, hard foam panels, semi-rigid foam molded products, and the like. It can also be applied to molding, injection molding, kneading mold, thermoplastic, two-component paint, flooring, etc. Mano, a new polyurethane molding method RIM (Reaction Injection M)
It can also be applied to the (olding) process.

The features and effects of the bituminized polyurethane and its manufacturing method of the present invention are summarized as follows.

(1) The bituminous type 9 polyurethane of the present invention has fine particles of petroleum pitch uniformly dispersed and bonded into the polyurethane. Petroleum pinch is a thermoplastic and has a high softening point, so it does not impair the heat resistance of polyurethane.

Since approximately 1/2 or more of petroleum pitch is fixed carbon, it has a stronger reinforcing effect than ordinary bituminous materials.

Since petroleum pitch is porous, it has good wet bonding with polyurethane and is integrated with the polyurethane, so petroleum pitch does not fall off. It is also non-contaminating. Petroleum pitch is chemically stable, and by adding bitumen to it, costs can be reduced and it has anti-aging effects.

+21 By pre-dispersing petroleum pitch into the polyisocyanate component, polyol component, or, if necessary, the plasticizer component of the polyurethane raw material, petroleum pitch can be mixed with these components and then pulverized and mixed through a grinder or the like to be dispersed. When this is done, each of the petroleum pitch fine particles (porous) is sufficiently wetted with these components and can be dispersed in a bonded state, so that the petroleum pitch is quickly dispersed when all of these raw materials are mixed. The petroleum pitch also speeds up the mixing of each ingredient. Furthermore, since petroleum pitch is chemically inert and stable, it does not harm the reaction of polyurethane, so it cannot be used as a raw material for polyurethane such as other chemicals, catalysts, crosslinking agents, blowing agents, auxiliaries, and other known substances. can be used to produce polyurethane foam and other polyurethanes by known methods.

Polyurethane raw material wets the porous structure of petroleum pitch.
Since they permeate, adsorb, etc. and react with each other, the affinity and bonding properties between petroleum pitch and polyurethane are extremely good, and it is possible to obtain an integrated bitumen-containing polyurethane.

Next, embodiments of the present invention will be explained using polyurethane foam as an example, but the present invention can also be applied to other polyurethanes.

The properties of the petroleum pitch used are as follows.

Example 1 Glycerin-based polyether polyol (average molecular weight approximately 3
000) A mixture of 50 parts by weight and 150 parts by weight of petroleum pitch sampler was mixed while crushing the petroleum pinch through a full-layer crusher to create a dispersion with a petroleum pitch concentration of 50% by weight. Petroleum pitch is a fine particle that is evenly and smoothly dispersed and does not settle.

A mixture of 50 parts by weight of the above polyol added to 100 parts by weight of this petroleum pitch polyol dispersion, 50 parts by weight of tolylene diisocyanate (TDI), 4 parts by weight of water, 0.2 parts by weight of triethylenediamine, and 0 parts by weight of stannous octoate. .3 parts by weight and 2 parts by weight of silicone stabilizer (bubble stabilizer) are placed in a container, quickly mixed and stirred with a stirrer, and poured onto a sheet to cause a foaming reaction. A polyurethane foam molded with polyurethane was obtained. This polyurethane foam is uniformly foamed and petroleum pitch is uniformly dispersed and bonded to the polyurethane structure. i! It is a good polyurethane foam that is clean, odorless, and shows no stickiness or staining.

Example 2 48 parts by weight of ffi agent DOP (di-2-ethylhexyl phthalate) was added with 252 parts by weight of petroleum pitch sample A. The product was pulverized and mixed through a full-layer crusher to disperse petroleum pitch into fine particles. Make a liquid (DOP dispersion of petroleum pitch).

Trimethylolpropane polyol (average molecular weight approximately 3
000) 100 parts by weight of the above DOP dispersion of petroleum pitch was added and mixed, and 0.2 M of triethylenediamine was added to 50 parts of TDI and 0.2 M of triethylenediamine.
1 part by weight, 0.3 parts by weight of Stanus octoate, and 2 parts by weight of silicone stabilizer are added to a container, quickly mixed and stirred with a stirrer, and poured onto a sheet to cause a forming reaction. 9. Polyurethane foam is molded with bituminized polyurethane. This urethane foam is uniformly foamed and petroleum pitch is uniformly dispersed and bonded to the polyurethane structure. It is a good polyurethane foam that is odorless and shows no stickiness or staining.

Example 3 Polyether polyol of glycerin-based propylene oxide and ethylene oxide adduct (average molecular weight 3.0
00) 100 parts by weight of petroleum pitch sample iFx 160
Add and mix parts by weight. 160 parts by weight of this and 4 parts by weight of water
Add 0.2 parts by weight of triethylenediamine, 0.3 parts by weight of stanas octoate, 1.5 parts by weight of silicone stabilizer (water-soluble silicone oil), and 48 parts by weight of TDI into all containers, The mixture was quickly mixed and stirred using a stirrer, poured onto a sheet, and subjected to a foam reaction to obtain a polyurethane foam molded from the bitumen-containing polyurethane of the present invention. In this polyurethane foam, petroleum pitch is uniformly dispersed and bonded to the polyurethane structure, and the foaming state is also good.

In addition, it is odorless, has no stickiness, and has no staining properties.

Example 4 20 parts by weight of aromatic process oil were added to 180 parts by weight of petroleum pitch sample A and mixed to produce granules.

Glycerin-based polyether polyol (average molecular weight 30
00) 65 parts by weight of the petroleum pitch sample A1 granules were added to 100 parts by weight and mixed. This, 48 parts by weight of TD, 4 parts by weight of water, and 0-2 Mt of triethylenediamine.
1.0 parts by weight, 0.3 parts by weight of Stanus octoate, and 1.5 parts by weight of Nuricon stabilizer were added to the whole container, mixed quickly with a stirrer, and poured onto a sheet to cause a foaming reaction. A polyurethane foam molded with the bituminized polyurethane of the invention was obtained. In this polyurethane foam, the petroleum pinch is uniformly dispersed and bonded to the polyurethane structure, and foaming is also good. It also has a good foam that is odorless, non-sticky, and non-staining.

Example 5 Glycerin-based polyether polyol (average molecular weight 30
00) A mixture of 50 parts by weight and 150 parts by weight of petroleum pitch sample flakes was ground and mixed using a total grinder to obtain a petroleum pitch dispersion polyol. A mixture of 100 parts by weight of this petroleum pitch dispersed polyol, 50 parts by weight of the above polyol, 72 parts by weight of Crude MDI, 4 parts by weight of water, 0.2 parts by weight of triethylenediamine, 0.3 parts by weight of stannous octoate, 1.5 parts by weight of silicone stabilizer and 0.2 parts by weight of foaming aid (cell opening agent) were added to a container, quickly mixed and stirred with a stirrer, and poured onto a sheet to cause a foaming reaction. A good polyurethane foam molded with the bituminous 9 polyurethane of the present invention was obtained.

Claims (2)

[Claims] (1) A bituminized polyurethane characterized by uniformly dispersing petroleum pitch in the polyurethane. (2) Of the polyurethane raw materials, petroleum pitch is added to one or more of the polyisocyanate component containing polyisocyanate as the main component, the polyol component containing polyol as the main component, or the plasticizer component containing plasticizer as the main component. A method for producing bituminous polyurethane, characterized in that petroleum pitch is uniformly dispersed in polyurethane by dispersing it in the form of fine particles, mixing and reacting polyurethane raw materials.