JPH02284915A - Purification of polyesteripolyol and polyurethane using same - Google Patents

Abstract

PURPOSE:To obtain the title polyol capable of giving polyurethanes excellent in resistance to bleeding and fungal attack by putting a polyesterpolyol to water treatment and/or n-hexane treatment to favorably remove low-molecular weight substances. CONSTITUTION:A polyesterpolyol is purified by water treatment and/or nhexane treatment. For example, the polyesterpolyol is dissolved in a solvent such as toluene, water at 30-50 deg.C is then added to the resulting solution followed by agitation and shaking. The solution is then left at rest and allowed to separate into two layers. The aqueous layer as the lower layer is removed, while water at 30-50 deg.C is added to the upper layer; these operations are repeated 3 to 4 times. Thence, both the water and solvent are removed at 110-120 deg.C/3-5mmHg while agitating, thus accomplishing the objective purification.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for purifying a polyester polyol and a polyurethane using the same that has excellent bleed resistance and mold resistance.

BACKGROUND OF THE INVENTION Conventionally, polyurethanes are made with combinations of polyester polyols, polyether diols, polyisocyanates, and chain extenders such as low molecular weight polyols or soamines.

Polyurethane using polyester polyol has excellent mechanical strength, heat resistance, oil resistance, etc., but has the drawbacks of poor water resistance, bleedability, and mold resistance. or,
Polyurethane using polyester polyol has excellent water resistance and mold resistance, but has problems with heat resistance, bleedability, light resistance, etc.

Therefore, various additives are used to improve the water resistance and mold resistance of polyurethane using polyester polyols, but there are problems such as decreased physical properties of the resulting molded products, discoloration, and bleeding.

The occurrence of bleeding caused by such short-term and long-term storage of polyurethane molded products has the disadvantages of contaminating the molded products, decreasing adhesion, deteriorating appearance, etc., and significantly lowering the commercial value. On the other hand, no method for purifying polyester polyol is known.

(Problems to be Solved by the Invention) As a result of intensive research to eliminate the bleeding of polyurethane using polyester polyol and to solve the problem of mold resistance, the present inventors purified and used the produced polyester polyol. In particular, they discovered that this problem could be solved and completed the present invention.

(Means for Solving Problem 11) That is, the present invention provides water treatment and/or treatment of polyester polyol.
The present invention also provides a method for purifying a polyester polyol, characterized by subjecting it to treatment with n-hexane, and a polyurethane using the obtained polyester polyol.

(Structure) The polyester polyol used in the present invention is produced by a conventional method, and preferably has a number average molecular weight of 300 to 5,000.

Glycol components used in the production of polyester polyols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol, 1,3 petile/glycol, 2.3 petile/glycol, 1.4 zotylene glycol, neo Pentyl glycol, l+5d/tanediol, 1,6 hexanediol, 3-methyl-1
, 5-bentanediol, 2-ethyl 1.3-hexanediol, 2,2.4-trimethyl 1.3-bentanediol,
1.8 octanediol, 1,9 nonanediol,
1.10 Aliphatic diols such as decanediol, cyclohexanedimethanol, cyclohexanediol, alicyclic diols such as hydrogenated bisphenol A, metaxylene glycol, xylene glycol, bishydroxyethoxypenze, bishydroxyethyl terephthalate, etc. These include aromatic diols, trimethylolethane, trimethylolgulon 4'7, aliphatic triols such as glycerin, etc., which are used in the production of ordinary polyester polyols, and these may be used alone or in combination of two or three types. used.

Examples of acid components used in the production of polyester polyols include aliphatic dicarboxylic acids such as malonic acid, geltaric acid, adipic acid, pimelic acid, azelaic acid, sepacic acid, dodeca/dicarboxylic acid, and hydrogenated dimer acid;
Unsaturated acids and anhydrides such as malic acid, maleic acid, dimer acid, aromatic dicarboxylic acids or anhydrides such as phthalic anhydride, isophthalic acid, terephthalic acid, etc. used in combination.

As the method for manufacturing the polyester polyol, a normal pressure method, a pressure method, a reduced pressure method, a solvent method using an aromatic hydrocarbon, etc. are employed.

When producing polyester polyol, it is not necessary to use a catalyst, but it is usually 0.0001% by weight based on the raw materials.
~0.5 wt. or 0.0003 to 0.02 wt. wt. of catalyst is used.

Examples of catalysts include Ll, Na, Rb, Ca,
Mg, Sr.

Zn, At, Ti, V, Cr, Mn, F@, C
o, Nl, Cu, Zr, Pd, an, S
b, Pb.

Metal oxides, chlorides, hydroxides, fatty acid salts such as acetic acid, Scheric acid, octylic acid, lauric acid, naphthenic acid, sodium methylate, sodium methylate, aluminum isoglopoxide, inglovir titanate, For normal esterification and transesterification reactions, such as alcolades such as n-butyl titanate and octyl titanate, 7 enolates such as sodium phenolate, organometallic compounds of metals such as AA, Ti, Sn, Zn, Zr, and Pb. Any catalyst used can be used.

The method for purifying the polyester polyol of the present invention involves treating a polyester polyol produced by a conventional method with water and/or n-hexane to reduce the molecular weight to about 60 to 50.
This objective can be achieved by removing low molecular weight substances.

A method for purifying low molecular weight substances by water treatment of polyester polyol is carried out in the following manner. First, -lyester polyol is dissolved in a solvent such as toluene or xine, water at 30° to 50°C is added thereto, thoroughly stirred and shaken at 30° to 50°C, and then left to stand to separate into two layers. The lower water layer is removed, water at 30' to 50°C is added to the upper layer, and the above operation is repeated 3 to 4 times. Then 110℃~120℃/
Completely remove water and solvent while stirring for 3 to 5 seconds and 1 mHg.

The amount of solvent used is preferably 25 to 100% by weight (abbreviated as %) based on the weight of the polyester polyol. If the amount of solvent used is less than 25%, the viscosity of the polyester polyol solution increases and in many cases the polyester polyol becomes solidified.

When the amount of solvent used is more than 100%, the viscosity of the polyester polyol solution becomes low and washing with water becomes easy, but it takes a long time to concentrate after washing with water.

The amount of water added is suitably 40 to 60% based on the weight of the polyester polyol solution. The amount of water added is 40
If the amount is less than 60% or more than 60%, both are undesirable because the time required for two-layer separation becomes longer.

Water treatment is carried out at a water temperature of 30 to 50°C, but if the temperature is below 30°C, it will take a long time to separate the two layers after water treatment, and if the water temperature is higher than 50°C, the -lyester polyol will be easily hydrolyzed. This is undesirable because it results in an increase in phosphoric acid value.

A small amount of low molecular weight substances can be removed with one water treatment, but in order to obtain the polyurethane of the present invention, 3 times of water washing is required.
~4 times is desirable.

The standing time after washing with water is usually 3 to 4 hours, but it is possible to add a trace amount of an acidic aqueous solution, such as a hydrochloric acid aqueous solution.
．． It can be compressed for 5-1 hours.

The n-hexane treatment is performed in the following manner. 50°~70
For the weight of polyester polyol heated to ℃,
Add 1 to 2 times the weight of n-hexane, heat to about 70°C, and stir for 1 hour while refluxing the n-hexane. After cooling to room temperature, the upper n-hexane layer is removed and the lower layer is treated at 100-5 mHg for 1 hour.

Especially when using a polyester polyol obtained by water treatment and/or n-hexane treatment,
It is possible to provide polyurethane that is tree-free and has excellent mold resistance.

The low molecular weight compounds used in producing the /IJ urethane of the present invention include polyols and polyamines having a molecular weight of about 50 to 250, such as ethylene glycol,
Diethylene glycol, 1.2-f robylene glycol, 1.3-propylene glycol, 1,3-butanediol, 2.3-butanol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1 , 5-bentanediol, neopentyl glycol, octanediol, nona/diol, aliphatic glycols such as decanediol, alicyclic fallols such as cyclohexaneol, cyclohexane dimetatool, bishydroxyethoyacibenzene, xylene glycol, etc. These include aromatic glycols. In addition, diamines include aliphatic diamines such as ethylene diamine, propylene diamine, and hexamethylene diamine, alicyclic diamines such as piperazine and inphoron diamine, xylem/soamine,
These include aromatic diamines such as 4.4'-methylenebisorthochloroaniline.

Furthermore, the polyisocyanates used in the present invention include aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate;
These include alicyclic diisocyanates such as inholo/diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated MDI, and aromatic diincyanates such as MDI, naphthylene diisocyanate, phenylene diisocyanate, and toridine diisocyanate.

Foaming agents used in the present invention include water and 7 Leon, foam stabilizers include silicone and funnel oil, and catalysts include DABCO and Sotutiltinolacrate, which are commonly used in the production of polyurethane foam. You can use what is provided.

The polyurethane of the present invention can be used for synthetic leather, spun rye,
It is extremely useful for non-porous or porous polyurethane elastomers such as Nistomer 7 Ohm.

(Effects) The purification method of the present invention is excellent in that it easily removes low molecular weight substances from polyester polyols. Polyurethane using polyester polyol obtained in this way has excellent bleed resistance and mold resistance. Thermoplastic polyurethane is used for synthetic leather, textiles, porous sheets, films, adhesives, various molded products, etc. It can be used in the following fields.

Next, examples of the present invention will be described, but the present invention is not limited to these in any way. Both "part" and "outside" in the text are based on weight.

Purification of polyester polyol> Example 1 (Polyester polyol-1) 1384 parts of ethylene glycol, 2920 parts of adipic acid 1. tetra n
-Pour 0.044 part of butyl titanate into a flask and conduct the reaction at 200°C while passing nitrogen gas, acid value 0.3
6. A polyester polyol having a hydroxyl value of 68.4 was obtained. Add 1500 parts of this polyester polyol to 1 part of toluene.
200 copies! After dissolving and bringing the temperature to about 40°C, add 1200 parts of ion-exchanged water at about 40°C, shake well, and let stand. After separating the two layers, remove the lower layer and add about 40% to the upper layer.
Add 1200 parts of ion-exchanged water at 0°C, shake well, and let stand. After repeating this operation 4 times, the upper layer liquid was
~b 0.32. Hydroxyl value 56.6? Diester polyol-1 was obtained. The amount of low molecular weight substances removed was approximately 2.7%.

Example 2 (Polyester polyol-2) 1402 parts of ethylene glycol, 2920 parts of adipic acid, tetra n-
0.044 parts of butyl titanate was charged into a flask, and the reaction was carried out at 200°C while nitrogen gas was passed through, resulting in an acid value of 0.34.
A polyester polyol having a hydroxyl value of 55.8 was obtained.

20 parts of n-hexane to 1,500 parts of polyester polyol
After adding 00 parts and thoroughly stirring and mixing, the mixture was maintained at about 70° C. for 1 hour while refluxing n-hexane. After cooling to room temperature, remove the upper layer and heat the lower layer to 100℃~110℃/
After treatment for 1 hour at 3 to 5 degrees H, If IJ ester polyol-2 having an acid value of 0.33 and a hydroxyl value of 54.5 was obtained. The amount of low molecular weight substances removed was approximately 0.3%.

Example 3 (-Reester Polyol-3) 2088 parts of 1.4f tandiol, 2920 parts of adipic acid, tetran
-A polyester polyol having an acid value of 0.30 and a hydroxyl value of 65.2 was synthesized in the same manner as in Example 1 using 0.050 parts of butyl titanate. Obtained polyester 1
Using 500 parts, water treatment was carried out in the same manner as in Example 1.
After repeating it twice, it was concentrated, acid value 0.28, hydroxyl value 56.7
Polyester polyol-3 was obtained. The amount of low molecular weight substances removed was approximately 2.5%.

All J4 (polyester polyol-4) 2752 parts of 1.6 hexanezoyl, 2920 parts of adipic acid, n
- Using 0.056 parts of tetrabutyl titanate, a polyester polyol having an acid value of 0.30 and a hydroxyl value of 62.5 was synthesized in the same manner as in Example 1. Using 1500 parts of this polyester polyol, water treatment was carried out four times in the same manner as in Example 1. After concentration, acid value 0.28, hydroxyl value 56
．． Polyester-Liol-4 of No. 5 was obtained. The amount of low molecular weight substances removed was approximately 2.0%.

Comparative Example 1 (Polyester Polyol-1') The untreated polyester polyol synthesized in Example 2 was designated as Polyester Polyol-1'.

Comparative Example 2 (Polyester Polyol-2') 1,026 parts of 1,4-butanediol, 1,460 parts of anopic acid, and 0.025 parts of tetra-n-butyl titanate were charged into a flask and treated in the same manner as in Example 1 to obtain an acid value of 0.34. , hydroxyl value 5
Polyester polyol-2' of 6.3 was synthesized.

Example 3 (Polyester polyol-3') Using 1363 parts of 1.6 hexa/diol, 1460 parts of adipic acid, and 0.028 parts of tetra-n-butyl titanate, acid was added in the same manner as in Example 1. A polyester polyol-3' having a value of 0.26 and a hydroxyl value of 55.3 was synthesized.

The removal amount and molecular weight distribution of low molecular weight substances of the polyester polyols of Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1.

<Synthesis of polyurethane> Example 5 Was it treated with water? Lyester Voriol-1986 parts, 1.
113 parts of 4-butanoyl, 460 parts of 4,4'-nophenylmethanezoisocyanate (abbreviated as MDI) to 100 parts
The thermoplastic polyurethane obtained by reacting at 180°C
After baking for 30 minutes, it is crushed and injection molded to a thickness of approximately 21 cm.
A sheet-like polyurethane elastomer No. 01 was prepared.

Example 6 l-lyester treated with n-hexane? Riolu 2
1023 parts, 1.4 butane oil 113 parts, MDI4
60 parts were reacted at 100° C., and the resulting thermoplastic polyurethane was cured at 180° C. for 30 minutes, crushed, and injection molded to produce a sheet-like polyurethane nidistomer with a thickness of about 2 squares.

Example 7 Polyester polyol-39 from which low molecular weight substances were removed
85 parts, 113 parts of 1.4-F tanned resin (abbreviated as 1.48G), and 460 parts of glass were reacted at 100°C, and a sheet-like polyurethane resin having a thickness of about 2 fl was prepared in the same manner as in Example 5. Created a streamer.

Example 8 Polyester polyol-49 from which low molecular weight substances were removed
88 parts, 1.48G 113 parts, German I 460 parts ioo℃
to a thickness of about 21 cII in the same manner as in Example 5.
A sheet-like polyurethane elastomer was created.

Comparative Example 4 Polyester polyol-1' 1000 parts, 1.4
113 parts of 8G and 460 parts of MDI were reacted at 100°C, and a sheet-like nidistomer having a thickness of 2 iris was prepared in the same manner as in Example 5.

Comparative Example 5 Polyester polyol-2'991 parts, 1, 4BG
113 parts of MDI and 460 parts of MDI were reacted at 100° C. in the same manner as in Example 5 to produce a sheet-like elastomer having a thickness of about 2 μ.

Comparative Example 6 Polyester I Lior-3'1010 parts, 1.4BG
113 parts of MDI and 460 parts of MDI were reacted at 100[deg.] C. in the same manner as in Example 5 to produce a sheet-like polyurethane disstomer having a thickness of approximately 2 mm.

Example 9 Water-treated polyester-diol-1394, 2 parts,
49.4 parts of 1.4-butanediol and 1190.8 parts of diol were reacted at 70°C in a dimethylformamide solvent to prepare a urethane solution with a resin content of 30 parts. This solution was coated on release paper and dried at 70°C for 2 hours to a thickness of about 0.
．． A film-like polyurethane disstomer No. 06- was prepared.

Example 10 n-hexane treated polyester polyol-240
9.2 copies, 1.4 BG 51.7 copies, MDI 1
A polyurethane solution was prepared by reacting 97.4 parts in a dimethylformamide (abbreviated as DMF) solvent at 70°C, and a film-like polyurethane distomer having a thickness of about 0.06 mm was prepared in the same manner as in Example 9.

Example 11 Polyester polyol-33 from which low molecular weight portions were removed
93.8 copies, 1.48G 49.4 copies, Germany I 190
．． 8 parts were reacted in a DMF solvent at 70° C. to prepare a polyurethane solution, and in the same manner as in Example 9, a film-like polyurethane entomer having a thickness of 0.06 mm was prepared.

Example 12 A polyurethane solution was prepared by reacting 2 parts of water-washed polyester polyol-4395, 49.5 parts of 1.4 BG, and 191.3 parts of MDI in a DMF solvent at 70°C, and the same method as in Example 9 was carried out. A film-like polyurethane disstomer having a thickness of about 0.06° C.m was prepared.

Comparative Example 7 Polyester polyol-1' 399.8 parts, 1.
Example 9
A film-like polyurethane elastomer having a thickness of about 0.060 mm was prepared in the same manner as described above.

Comparative Example 8 Polyester polyol-2' 396.2 parts, l,
DM 4-BG 49.6 copies, Mukai I 191.2 copies
Prepare a polyurethane solution by reacting at 70°C in F solvent,
A film-like polyurethane elastomer having a thickness of 0.06 a was prepared in the same manner as in Example 9.

Comparative Example 9 Polyester biliol-3' 403.8 parts, 1,
4-8051 parts and 1195.4 parts of auxiliary were added to 70% of D■゛ solvent.
A polyurethane solution was prepared by reacting at 0.degree. C., and a polyurethane elastomer film having a thickness of about 0.06 m was prepared in the same manner as in Example 9.

Tables 1 and 2 show the physical properties, bleed properties, and mold resistance of the polyurethanes obtained in Examples 5 to 12 and Comparative Examples 4 to 9.

1.Measurement method 1.Physical properties hardness, tensile strength, elongation, and tear strength are JIS K-6301
Measurement was carried out at 23° C. and RH 60%.

2. Bleed resistance test 14X10X0.2111 sheet at 40℃RH95%
The sample was placed in a constant temperature and humidity chamber for 30 days, and the presence or absence of bleeding on the surface was visually determined.

3. Mildew resistance test method This was carried out using a modified method of JIS-Z-2911.

Place a 30x30n specimen sterilized by soaking it in boiling water on a potato chef roast agar (PSA) medium in a petri dish, sprinkle the mixed spore suspension 1- uniformly on the surface, and store it at 28°C for 28 days to remove mold. The occurrence was observed.

The test bacteria are as follows.

0 Aspergillus skewers for PSA medium
nig@r) ATCC6275 o! = Sirium citrinum (P*nieill)
lumcitrinum) ATCC9849 0 Rhlzopus nl
grlcaus) S, N, 320 Cladosporium harpalum (C1 Todospor
IAM @F 5170 Chaetomium glo
bosum) ATCC6205/Z+\,-'~17,Z--'//Example 13 1250 parts of polyester polyol-A/- and 80 parts of MDI were reacted at 75 to 80°C to form a polyurethane prepolymer with an NGO equivalent weight of 850. Prepared. This prepolymer 200
2.0 parts of ion-exchanged water, 0.05 parts of triethylenediamine (abbreviated as DABCO),
゛Add 3.05 parts of a mixed solution mixed with 1.0 part of a silicone foam stabilizer and adjusted to 80°C, mix vigorously, and pour into the heated chamber.9. After pouring, the mold was closed and placed in a dryer at 100℃ for 2 hours.
The mixture was aged for 0 hours to prepare a sheet-like cellular polyurethane elastomer having a thickness of about 6 mm.

Example 14 1300 parts of polyester polyol was reacted with 78 parts of 1.5 naphthylene diisocyanate at 115 to 125°C to prepare a polyurethane prepolymer having an NGO equivalent weight of 848.

200 parts of this prepolymer was adjusted to 80°C, and 2.0 parts of ion-exchanged water, 0.05 part of triethylenecyamine, and 1.0 part of a silicone foam stabilizer were mixed thereto and the temperature was adjusted to 80°C. 3.05 parts of a homogeneous solution was added, mixed vigorously and poured into the mold. After pouring, the mold was clamped and placed in a dryer at 100° C. for 20 hours to ripen, thereby preparing a sheet-like cellular polyurethane nidistomer with a thickness of about 611 m.

Comparative Example 10 MDI8 in 250 parts of polyester polyol-1'
0 part was reacted at 75 to 80°C to prepare a polyurethane prepolymer having a weight of 1k852 per NCO.

200 parts of this prepolymer was adjusted to 80°C, and 2.0 parts of ion-exchanged water, 0.05 part of Trietele/Noamine, and 1.0 part of silicone foam stabilizer were mixed thereto and the temperature was adjusted to 80°C. 3.05 parts of the homogeneous solution was added, mixed vigorously and poured into the mold. After injection, the mold was closed and placed in a dryer at 100℃.
The mixture was aged for 0 hours to produce a sheet-like cellular polyurethane elastomer F1i1 having a thickness of approximately 5 mm.

Comparative Example 11 78 parts of polyester polyol-1'300 parts K 1.5 naphthylene/twin cyanate were reacted at 115 to 125°C to prepare a polyurethane prepolymer having an NCO equivalent of -ji 850.

200 parts of this prepolymer was adjusted to 80°C, and mixed with 2.0 parts of io/exchanged water, 70.05 parts of triethylene diamide, and 1.0 part of a silicone foam stabilizer, and the temperature was adjusted to 80°C. 3.05 parts of the homogeneous solution was added, mixed vigorously, and poured into the mold. After injection, the mold was clamped and placed in a dryer at 100℃ for 20 minutes.
A sheet-like cellular polyurethane elastomer having a thickness of about 6 mm was prepared by aging for a long time.

Table 4 shows the measurement results of physical properties, bleed resistance, and mold resistance of Example 13.14 and Comparative Example 10.11.

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Claims (1)

[Claims] 1. A method for purifying a polyester polyol, which comprises treating the polyester polyol with water and/or n-hexane. 2. A polyurethane using the polyester polyol obtained in claim 1.