JPS617321A - Novel prepolymer, its resin and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a prepolymer useful as a moisture-curable one-pack type polyurethane resin, etc., free from irritant smell nor toxicity, stable to heat and light, and resistant to yellowing, by reacting a specific isocyanate component with a polyester diol at a specific ratio. CONSTITUTION:The objective prepolymer of formula I {R<1>-R<3> are -N=C=O or group of formula II [R<4> and R<5> are -N=C=O or group of formula III (Z is trifunctional residue of formula IV; Q is residue obtained by removing H atoms from both terminals of a bifunctional polyester diol)] provided that at least one of R<1>-R<3> is group of formula II} can be produced by reacting (A) 1,8-diisocyanato-4-isocyanatomethyloctane with (B) a bifunctional polyester diol having a number-average molecular weight of 200-10,000 at an equivalent ratio (NCO/ OH) of 2-20, preferably at 60-140 deg.C.

Description

Detailed Description of the Invention "Object of the Invention" [Industrial Application Field] The present invention is a novel polyester urethane prepolymer used for foaming materials, coating materials, adhesives, casting resins, etc. using polyurethane resins. and its uses.

[Conventional technology]

It has been known that aliphatic polyisocyanates can be used as raw materials for non-yellowing polyurethane resins with excellent weather resistance. Representative products of these non-yellowing polyisocyanates include hexamethylene diisocyanate (hereinafter referred to as HMDI) and 2.2.4-(or 2,4,4-
)) There are diincyanate monomers such as lymethylhexamethylene diisocyanate and inphorone diisocyanate (hereinafter referred to as IPDI), but since these have relatively high vapor pressure at room temperature, their irritation and toxicity due to inhalation pose problems. Therefore, commonly used aliphatic I diisocyanates are adducts obtained by reacting HMOI, IPDI, etc. with diols such as butanediol or triols such as trimethylolpropane, or biurets of water, tertiary butanol, etc. It is oligomerized into a biuret form reacted with a chemical agent or an incyanurate form trimerized with a catalyst, and the vapor pressure is lowered by removing unreacted monomers.

These aliphatic polyisocyanate oryzamers generally have an average molecular weight of about 600 to 1,500, and are used as curing agents for paints in combination with base agents such as neoconcentrations of 11 and ols.

On the other hand, in the field of polyurethane resins, in addition to curing agents for paints, for example, in the field of foaming, adhesives, moisture-curing paints, etc., we are developing products with even higher average molecular weights and physical properties with improved compatibility and workability. In many cases, polyester urethane prepolymers having the following properties are required, and the demand for non-yellowing properties is increasing in such fields.

Such polyester urethane prepolymers include those made by reacting polyester diols or triols with large molecular weights of diifodiisocyanate monomers such as HMDI and IPDI, and those made by reacting oligomers of the diisocyanate with polyester diols. .

[Target day reference - 1) Go 9 family, ↓ > drufushino 5 reference point 7] However, when it comes to the combination of diincyanate monomer, diol, or triol, it can be used relatively freely depending on the purpose. Although it is possible to obtain physical properties such as viscosity, NOO content, number of functional groups, and molecular weight, diisocyanate monomer inevitably remains in the reaction product, and its irritation and
Use is restricted due to toxicity.

On the other hand, reaction products of Oryzamer and polymeric diols such as adducts, biurets, and isocyanurates alleviate the above-mentioned toxicity problem of diisocyanate monomers; NO above
Because there are many polygons with O groups, it is very easy to gel during prepolymer production, and even if gelation does not occur, the viscosity may be too high, making it difficult to create a prepolymer with physical properties that suit the purpose. The disadvantage is that it is difficult to

Therefore, in this industry, we use non-yellowing polyesters that do not have the irritation and toxicity problems of diisocyanate monomers and can freely select physical properties depending on the purpose. The appearance of urethane prepolymers has been awaited.

The object of the present invention is to provide a novel polyester urethane prepolymer that can meet these demands.

"Structure of the Invention" [Means for Solving the Problems] As a result of intensive research by the present inventors to overcome the above problems,
1.8-1 Ink AnnatoWe have completed the present invention by discovering that the object can be achieved with a new compound, a reaction product of 4-isocyanatomethyloctane and a difunctional polyester diol, which has not been described in any literature.

That is, the present invention relates to a polyester urethane prepolymer consisting of a compound group represented by general formula (1), R'-0H2
-CIH2 0HM 0H-OH2 0H2 0H2-
OH2 R"0H.-几3
...(I) [General formula (n's R"l R' in 11)
each represents a -N=O=O group or the following general formula (It), and -NH-co-o -Q-0-00 -NH -Z-a
'BS... (IF) and the prepolymer always contains at least one of R', R'', and R'' of the general formula (If), where the general formula ( B4.
.

NOO...(2) In addition, 2 in general formulas (II) and (to) represents a trifunctional residue of the formula, and Q is a residue obtained by removing both terminal hydroxyl groups from a difunctional polyester diol. shows. ] and its uses.

The novel prepolymers according to the invention are prepared by reacting 1,8-diisocyanato-4-isocyanatomethyloctane with difunctional polyester diols.

1,8-diisocyanato-4-incyanatomethyloctane is disclosed in, for example, JP-A-56-127341.
, 1,8--,) can be obtained by reacting amino-4-aminomethyloctane or a salt thereof with phosgene.

2 sensuality, 1? Examples of the liester diol include carboxylic acids such as phthalic acid, adipic acid, azelaic acid, and henanosinic acid, ethylene glycol, zolopylene glycol, 1.3--)tanediol, 1.4-butanediol, neopentyl glycol, Polycondensation reaction products with diols such as 1,6-hexa/diol, diethylene glycol, and dipropylene glycol, and ring-opening polymerization reaction products of cyclic esters such as ε-caprolactone using the above diols as an initiator. etc. Also preferably used are oil-based diols, such as castor oil, which is obtained by treating one hydroxyl group from a triglyceride of a fatty acid having a hydroxyl group by a dehydration reaction or the like. These polyester diols can also be mixed and used as appropriate.

The reaction is generally carried out at room temperature to 180°C, preferably at a temperature of 60 to 1
It is carried out at 40°C. If the reaction temperature is too low, it will take a long time to complete the reaction, and if the reaction temperature is too high, side reactions will occur. Inert solvents such as aromatic hydrocarbons such as butyl acetate, ethyl acetate, esters such as ethylene glycol monoethyl ether acetate, ketones such as 2-sitanone, 4-methyl-2-pentanone, etc.; A reaction promoting catalyst such as a tertiary amine compound or a tertiary amine compound can be used.

The charging ratio of 1,S-diisocyanato-4-incyanatomethyloctane and polyester diol used in the reaction must be carefully selected depending on the purpose, as it has a large effect on the physical properties of the prepolymer produced.
The equivalent ratio of 2 to 2G is selected. The smaller the ratio of NCo10H, the higher the average molecular wave and viscosity of the produced prepolymer, and the lower the NCo content. , and 20 or more, 1,8- by prepolymerization
The modification effect of diisocyanato-4-isocyanatomethyloctane is poor.

[Effect]

Although the prepolymer thus obtained is a non-yellowing type that is stable against heat and light, it does not contain any relatively highly volatile diisocyanate monomers such as HMDI and IPDI, so it can be selected for irritating odors and inhalation. This makes it possible to freely develop physical properties such as molecular weight, viscosity, NCo content, compatibility with other resins, and curing properties depending on the purpose.

This prepolymer is used as an incyanate component of a secondary curable non-yellowing polyurethane resin and as a -grade non-yellowing moisture curable resin.

When used as an incyanate component of a two-component polyurethane resin, for example, an acrylic polyol.

Polyester polyols, polyether polyols, hydroxyl-terminated polyolefin polyols and their hydrogenated products, epoxy polyols, polycarzenate polyols, etc. - resins with two or more hydroxyl groups in the molecule, 3.3'- It is cured in combination with polyvalent active hydrogen compounds such as polyamines such as dichloro-4,4'-diaminodiphenylmethane and its modified products. The resulting polyurethane resin can be used in a wide variety of applications, including foams, casting resins, adhesives, paints, sealants, flooring materials, nidistomers, and coating agents.

When the prepolymer of the present invention is used as a one-component non-yellowing moisture curable resin, one having a relatively low NOO content of 12% or less is effective. Such a prepolymer with a low NCO content is prepared by combining 1,8-diisocyanato-4-isocyanatomethyloctane and a polyester polyol with NCO.
It can be obtained by reacting at a molar ratio of eoloH of 4.5 or less.

The obtained prepolymer can be used in the fields of paints, adhesives, flooring materials, sealants, coatings, etc. by adding catalysts, pigments, and other additives as necessary in a solvent-free system or a solvent-diluted system. Useful as a mold moisture curing resin.

The present invention will be specifically explained below using examples.

Note that the measuring equipment and measuring method used in the examples are as follows.

(Measuring equipment) Viscosity: Emira circuit viscometer Infrared absorption spectrum (IR): JASCO Corporation I
R-1 Gel permeation chromatography (GPO)
: Takasugi Seisakusho LO-3A (Column H8G-40+H8G
-20+H8G-15) (Measurement method) NOO content: Measured according to JI8 K-1556.

Average molecular weight: Calculated from a GPO calibration curve using polystyrene standards.

Paint film physical properties: Decayed according to JI8 K-5400.

Example 1 Polycasilolactone diol 159 with molecule t 1200
f and 1,8-diisocyanato-4-incyanatomethyloctane 100f and dibutyl as a catalyst.The viscosity of the obtained prepolymer at 25°C is 6000 cps, N
The eo content was 14.1% by weight.

From GPO analysis, this product contains 19-fold strains of 1,8-diisocyanato-4-isocyanatomethyloctane and 81
The weight average molecular weight of the entire prepolymer is 6,500. The number average molecular weight was 1000.

In addition, infrared absorption spectrum analysis of the obtained prepolymer revealed that Neo group absorption was at 2240 tM-'', and Neo group absorption was at 1720 tM-''.
6++-'' shows an overlapping absorption of an ester bond and a urethane bond, and 1520(!l11-' shows an amide absorption caused by a urethane group. Together with the GPO results, it can be concluded that the structure has the structure of general formula (1). confirmed.

This product had no odor at all at room temperature and could be handled safely.

FIG. 1 shows an infrared absorption spectrum, and FIG. 1 shows a GPO elution curve of this prepolymer.

Example 2 Polycasilolactone diol 238f with a molecular weight of 1200
and 100 f of 1,8-diisocyanato-4-incyanatomethyloctane were diluted to 50% by weight with toluene, and 0.005 f of dibutyltin dilaurate was added as a catalyst.
The reaction was carried out at 0°C for 6 hours.

(NCO/6H molar ratio = 3) 2 of the obtained prepolymer solution with a nonvolatile content of 50'Mi%
Viscosity at 5℃ is 110cpa, NOO content is 4
．． It was 1% by weight.

From GPO analysis, it contains about 8% by weight of 1,8-diisocyanato-4-isocyanatomethyloctane and about 9% by weight of 1,8-diisocyanato-4-isocyanatomethyloctane.
Made from 2% by weight of a polymer with a molecular weight of 1000 or more,
The weight average molecular weight of the entire prepolymer was 18,000, and the number average molecular weight was 2,100.

In addition, the infrared absorption spectrum is 2240 m as in Example 1.
-'', 1720y+-1, 1520cm-' showed characteristic absorption.

Example 3 596t polycasilolactone diol with a molecular weight of 3000 instead of polycasilolactone diol with a molecular weight of 1200
The reaction was carried out in the same manner as in Example 2 except that . (N
OO10H equivalent ratio = 3) The viscosity at 25°C of the obtained sol polymer solution with 50 layers of non-volatile content is 110 cps
%NOO content was 4.1% by weight.

Example 4 Polyester diol 82t and 1.8 with a molecular weight of 1100, which are polycondensation products of adipic acid and ethylene glycol
-diisocyanato-4-isocyanatomethyloctane 1
00f was diluted to 50% by weight with dityl acetate, 0.01 t of dibutyltin silalate was added, and the mixture was reacted at 100° C. for 2 hours. (NOOloH"k amount ratio = 8) 25% of the obtained prepolymer solution with a non-volatile content of 50% by weight.
Viscosity at °C is 10 cps, NCo content is 11
．． It was 2% by weight.

GPO analysis showed that this product contained 18.5% by weight of 1,8-diisocyanato-4-incyanatomethyloctane and 8
It consists of 1.5% by weight of a polymer with a molecular weight of 1000 or more, and the weight average molecular weight of the entire prepolymer is 3400. The number average molecular weight was 600.

Example 5 45v of castor oil diol (Neelik H-53: Ito Oil Co., Ltd.) and 100f of 1,8-diisocyanato-4-isocyanatomethyloctane were mixed with 0.0f of dibutyltin silalate.
The reaction was carried out at 100° C. for 2 hours using 039 as a catalyst.

The viscosity of the obtained prepolymer at 25°C is 95 c
ps, the NCo content was 31.5'%.

GPO analysis showed that this product contained 49.2% by weight of 1,8-diisocyanato-4-incyanatomethyloctane and 5
It consists of 0.8% by weight of a polymer with a molecular weight of 1000 or more, and the weight average molecular weight of the entire prepolymer is 1200. The number average molecular weight was 380.

Comparative Example 1 In place of 1t s I isocyanato-4-isocyanatomethyloctane 1001F, a biuret body of HMDI (N00 inclusion = 23.3%, viscosity at 25°C 19
The reaction was carried out in exactly the same manner as in Example 2, except that 2162 ml of 00 cp) was used.

The aqueous system had Nco10n/z ratio=3 as in Example 2, but gelatinized after heating at 100° C. for 1 hour.

Comparative Example 2 A reaction was carried out in exactly the same manner as in Example 2, except that 10Of of HMDI was used in place of 10Of of 1,8-diisocyanato-4-isocyanatomethyloctane.

The obtained prepolymer has a viscosity of 2100c at 25°C.
p, NCo content was 10.2% by weight. This product contained 15.6% by weight of free HMDI and had a strong pungent odor.

Example 6 The prepolymer obtained in Example 1 and acrylic polyol (Acridic A-801: manufactured by Dainippon Ink and Chemicals) were blended at a N0O10H ratio of i and o, and ethyl acetate/toluene/butyl acetate was added as a thinner to this. /Xylene/
Cellosolve acetate (weight ratio = 3 o73 oz' 2 o
/15/5) was added, and the temperature was adjusted to 720°C for 20 seconds using a FourP Cobbuna 4. The resulting coating solution was applied to a dry film thickness of 50 μm using an air spray gun, and the physical properties were measured after standing for 10 days at 20° C./65% RH.

The resulting polyurethane resin coating had excellent performance as shown in Table 1.

Example 7 0.3 t of 100 rK dibutytin dilaureta of the prepolymer obtained in Example 2 was added, diluted with thinner, and painted in the same manner as in Example 8.

The resulting coating film was moisture cured within 25 hours at 20°C/65RH%, and its physical properties after standing for 10 days under the same conditions were excellent as shown in Table 1.

Table 1 Example 8 Prepolymer obtained in Example 1 and polypropylene glycol tra N0O10 with a molecular weight of 2000 and a hydroxyl value of 56
Blended with an H ratio of 1.0 and heated at 80°C and 20°C in a mold with an open top.
The polyurethane resin was molded by heating and curing for several minutes. The prepolymer and polypropylene glycol were uniformly miscible with each other, and the obtained polyurethane resin was also colorless and transparent.

Comparative Example 3 Instead of the prepolymer of Example 1, H used in Comparative Example 1 was used.
A polyurethane resin was obtained in the same manner as in Example 10, except that a billet body of MDI was used. The biuret body of HMDI and polypropylene glycol were not uniformly miscible with each other, and the obtained polyurethane resin was also cloudy and opaque.

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectrum of the same prepolymer obtained in Example 1, and FIG. 2 shows the GPO elution curve of the prepolymer obtained in Example 1. Patent applicant Asahi Kasei Kogyo Co., Ltd. Figure 2 to'IQ" 20001000300 (molecular weight) Procedural amendment (spontaneous) July 1, 1980 Commissioner of the Japan Patent Office Manabu Shiga L Case indication 1988 Patent Application No. 126438
No. 2 Name of the invention New prepolymer and its reconversion and manufacturing method 3, Relationship with the case of the person making the amendment Patent producer No. 21F6, Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture (003) Asahi Kasei I-Gyo Co., Ltd. & Amendment Contents (1) Please fill in the column for detailed explanation of the invention in the specification as shown below.
correct. (2) Table 1, page 18, test item column “Glossiness (60°
"Gloss)" is corrected to "Glossiness (60° cross)". that's all

Claims (4)

[Claims] (1) Polyester urethane prepolymer consisting of a group of compounds represented by the general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) [R^1, R^2, in the general formula (I), R^3 each represents a -N=C=O group or the following general formula (II), ▲There are numerical formulas, chemical formulas, tables, etc.▼...(II) And in the prepolymer, R^1, R At least one of ^2 and R^3 always contains the general formula (II), where R^4 and R^5 in the general formula (II) are each -N=C =O group or the following general formula (III), ▲
There are mathematical formulas, chemical formulas, tables, etc.▼...(III) And Z in general formulas (II) and (III) is the formula▲mathematical formula,
There are chemical formulas, tables, etc. ▼ indicates a trifunctional residue, and Q indicates a residue obtained by removing both terminal hydroxyl groups from a difunctional polyester diol. ] (2) A polyurethane resin characterized by using a prepolymer represented by general formula (I) as a polyisocyanate component (3) One-component moisture-curing polyurethane resin whose main component is a prepolymer represented by general formula (I) (4) 1,8-diisocyanato-4-isocyanatomethyloctane and a bifunctional polyester diol having a number average molecular weight of 200 to 10,000 at a NOO/OH equivalent ratio of 2 to 2.
A method for producing a prepolymer represented by general formula (I), which is characterized by reacting in step 20.