Polyoxyalkylene polyols, derivatives thereof, and process for producing the polyoxyalkylene polyols

• US 6,207,794 B1
• Filed: 12/17/1998
• Issued: 03/27/2001
• Est. Priority Date: 05/28/1997
• Status: Expired due to Term

• Current Assignee: Mitsui Chemicals & SKC Polyurethanes Inc.
• Original Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Inventors: Yamasaki, Satoshi, Watanabe, Hitoshi, Matsumoto, Shinsuke, Aoki, Masaaki, Tamura, Satoshi, Yamazaki, Fumio, Matsufuji, Mikio, Hara, Yasunori, Nishikawa, Ariko, Izukawa, Tsukuru, Nobori, Tadahito, Takaki, Usaji
• Primary Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US09/202,559
• Time in Patent Office: 831 Days
• Field of Search: 524/507, 524/589, 524/590, 528/44, 528/65, 528/85, 528/408, 568/620
• US Class Current: 528/408
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/4866 having a low unsaturation value
• CPC Class Codes: C08G 18/5024 containing primary and/or secondary amino groups
• CPC Class Codes: C08G 18/632 onto polyethers
• CPC Class Codes: C08G 18/6685 with compounds of group C08G18/3225 or polyamines of C08G18/38
• CPC Class Codes: C08G 65/2663 Metal cyanide catalysts, i.e. DMC's
• CPC Class Codes: C08G 65/2675 Phosphorus or compounds thereof
• CPC Class Codes: C08G 65/30 Post-polymerisation treatment, e.g. recovery, purification, drying

Abstract

The present invention is a polyoxyalkylene polyol, its manufacture method, and derivatives, wherein: it is obtained using a phosphazenium compound as a catalyst; the hydroxyl value is 2˜200 mgKOH/g; total degree of unsaturation is 0.0001˜0.07 meq./g; the head-to-tail bond selectivity of the polyoxyalkylene polyol is 95 mole %; and when the maximum height of the peak of GPC elution curve is set to be 100%, W₂₀ is defined as the peak width at the 20% peak height, and W₈₀ is defined as the peak width at 80% peak height, the ratio of W₂₀/W₈₀ is 1.5 or greater, and less than 3.

Claims

1. A polyoxyalkylene polyol obtained by using a phosphazenium compound as a catalyst wherein said polyoxyalkylene polyol has:

a hydroxyl value (OHV) of 2˜

200 mgKOH/g;

a total degree of unsaturation (C═

C) of 0.0001˜

0.07 meq./g;

a head to tail (H-T) bond selectivity of the polyoxyalkylene polyol resulting from addition polymerization of propylene oxide is 95 mole % or greater;

W₂₀/W₈₀ is 1.5 to less than 3; and

a residual amount of said phosphazenium compound catalyst is 150 ppm or less.

2. A polyoxyalkylene polyol as described in claim 1, wherein:

said phosphazenium compound is a salt of a phosphazenium cation shown in formula (1) and an inorganic anion;

 

or it is a phosphazenium compound shown in formula (2)

wherein in formulas (1) and (2), a, b, c, d are integers from 0˜

3 where all four are not 0;

R is a hydrocarbon group of the same type or different types with a carbon number of 1˜

10 and two R'"'"'s from the same nitrogen atom can be bonded to form a ring structure;

in formula (1), r is an integer from 1˜

3 and is the number of phosphazenium cations;

T^r−

represents an inorganic anion with a valency of r; and

Q⁻

in formula (2) represents an anion selected from the group consisting of hydroxy anion, alkoxy anion, aryloxy anion, and carboxy anion.

3. A polyoxyalkylene polyol as described in claim 1, wherein:

OHV is 9˜

120 mgKOH/g;

C═

C is 0.0001˜

0.05 meq./g;

H-T bond selectivity is 96 mole % or greater; and

W₂₀/W₈₀ is 2 to, less than 3.

4. A polyoxyalkylene polyol as described in claim 1, wherein:

C═

C is 0.0001˜

0.03 meq./g.

10. A polymer dispersed polyol, wherein:

polymer particles are dispersed within a polyol;

said polyol is a polyoxyalkylene polyol described in claim 1;

the concentration of said polymer particles is 5˜

60 weight %.

11. A polymer dispersed polyol as described in claim 10, wherein:

the concentration of said polymer particles is 10˜

50 weight %.

12. A polymer dispersed polyol as described in claim 10, wherein:

said polymer particles are a polymer obtained from at least one of ethylenically unsaturated monomers selected from the group consisting of acrylonitrile, styrene, acrylamide, and methyl methacrylate.

13. An isocyanate terminated prepolymer, wherein:

said isocyanate terminated prepolymer results from reacting a polyol and an isocyanate;

said polyol is a polyoxyalkylene polyol described in claim 1; and

isocyanate group content of said isocyanate terminated prepolymer is 0.3˜

30 weight %.

14. An isocyanate terminated prepolymer as described in claim 13, wherein:

the CPR of said polyoxyalkylene polyol is 5 or less.

15. An isocyanate terminated prepolymer as described in claim 13, wherein:

isocyanate group content is 0.4˜

20 weight %.

16. An isocyanate terminated prepolymer as described in claim 13, wherein:

the content of free isocyanate compound is 1 weight % or less.

17. An isocyanate terminated prepolymer, wherein:

said isocyanate terminated prepolymer results from reacting a polyol and an isocyanate;

said polyol is a polymer dispersed polyol described in claim 10; and

isocyanate group content of said isocyanate terminated prepolymer is 0.3˜

30 weight %.

18. An isocyanate terminated prepolymer as described in claim 17, wherein:

isocyanate group content is 0.4˜

20 weight %.

19. A polyurethane resin, wherein:

said polyurethane resin results from reacting a prepolymer and a chain extender; and

said prepolymer contained at least 60 weight % of an isocyanate terminated prepolymer described in claim 13 or 17.

20. A polyurethane resin described in claim 19, wherein:

the content of free isocyanate compounds in said isocyanate terminated prepolymer is 1 weight % or less.

21. A polyurethane resin described in claim 19, wherein:

said prepolymer is a mixture, comprising;

an isocyanate terminated prepolymer described in claim 17; and

an isocyanate terminated prepolymer which has a free isocyanate compound content of 1 weight % or less, and which is obtained from at least one type of polyol selected from the group consisting of polytetramethylene glycol, polyethylene adipate, and polycaprolactone polyol.

22. A polyoxyalkylene polyamine, wherein:

said polyoxyalkylene polyamine is a polyol which has its terminal hydroxyl group aminated; and

said polyol is a polyoxyalkylene polyol described in one claim from claims 1˜

4.

23. A polyoxyalkylene polyamine as described in claim 22, wherein:

the active hydrogen value is 5˜

180 mgKOH/g;

the oxypropylene group content is at least 50 mole %; and

H-T bond selectivity of the oxypropylene group bond is at least 95 mole %.

24. A polyurethane urea resin, wherein:

said polyurethane urea resin is obtained by a reaction of a polyisocyanate compound and a polyol which contained polyoxyalkylene polyamine of claim 22.

5. A manufacture method for a polyoxyalkylene polyol, wherein:

in the presence of a salt of a phosphazenium cation represented by formula (1) and an inorganic anion and an alkali metal salt or an alkali earth metal salt, or in the presence of a phosphazenium compound represented by formula (2) and an active hydrogen compound, the amount of said phosphazenium compound represented by formulas (1) or (2) is prepared in the range of 1×

10<sup>−

4</sup>˜

5×

10<sup>−

1</sup> moles for every 1 mole of active hydrogen compound;

under the conditions of reaction temperature 15˜

130°

C. and maximum reaction pressure of 882 kPa (9 kgf/cm²), alkylene oxide is addition polymerized to produce a crude polyoxyalkylene polyol;

next, removal of said phosphazenium compound which is contained in said crude polyoxyalkylene polyol is conducted by a method selected from the group consisting of methods e˜

h described below;

e. for every 100 weight parts of said crude polyoxyalkylene polyol, 1˜

40 weight parts of water is added;

next, for every 1 mole of phosphazenium compound in the crude polyoxyalkylene polyol, 0.5˜

8 moles of inorganic acid or organic acid is added;

the phosphazenium compound is neutralized at 50˜

130°

C.;

next, for every 100 weight parts of crude polyoxyalkylene polyol, 0.005˜

2.5 weight parts of adsorbent is added;

water is removed through vacuum processing; and

phosphazenium salt and adsorbent are removed by filtration;

f. for every 100 weight parts of said crude polyoxyalkylene polyol, 1˜

40 weight parts of a mixture of water and an organic solvent which is inactive to polyoxyalkylene polyol is added;

next, for every 1 mole of phosphazenium compound in said crude polyoxyalkylene polyol, 0.5˜

8 moles of inorganic acid or organic acid is added;

said phosphazenium compound is neutralized at 50˜

130°

C.;

next, for every 100 weight parts of crude polyoxyalkylene polyol, 0.005˜

2.5 weight parts of adsorbent is added;

water and organic solvent are removed by vacuum processing; and

phosphazenium salt and adsorbent are removed by filtration;

g. for every 100 weight parts of crude polyoxyalkylene polyol, 1˜

200 weight parts of water only or a mixture of water and organic solvent which is inactive to polyoxyalkylene polyol is added;

liquid separation is conducted; and

after rinsing, water and organic solvent are removed by vacuum processing; and

h. for every 100 weight parts of crude polyoxyalkylene polyol, 20˜

200 weight parts of water is added; and

after bringing into contact with an ion exchange resin at 15˜

100°

C., water is removed by vacuum processing, wherein formulas (1) and (2) are as follows;

 

or it is a phosphazenium compound shown in formula (2)

wherein in formulas (1) and (2), a, b, c, d are integers from 0˜

3 where all four are not 0;

R is a hydrocarbon group of the same type or different types with a carbon number of 1˜

10 and two R'"'"'s from the same nitrogen atom can be bonded to form a ring structure;

in formula (1), r is an integer from 1˜

3 and is the number of phosphazenium cations;

T^r−

represents an inorganic anion with a valency of r; and

Q⁻

in formula (2) represents an anion selected from the group consisting of hydroxy anion, alkoxy anion, aryloxy anion, and carboxy anion.

6. A polyoxyalkylene polyol manufacture method as described in claim 5, wherein:

in methods e and f described above, for every 1 mole of said phosphazenium compound in said crude polyoxyalkylene polyol, 0.5˜

2.5 moles of said inorganic acid or organic acid, and for every 100 weight parts of said crude polyoxyalkylene polyol, 0.005˜

1.5 weight parts of said adsorbent are added.

7. A polyoxyalkylene polyol manufacture method as described in claim 5, wherein:

in chemical formula (1), a, b, c, d, and r are all 1, and T⁻

is a chlorine ion.

8. A polyoxyalkylene polyol manufacture method as described in claim 5, wherein:

in chemical formula (2), a, b, c, d, and r are all 1, and Q⁻

is a hydroxy anion.

9. A polyoxyalkylene polyol manufacture method as described in claim 5, wherein:

the amount of phosphazenium compound represented by formula (1) or (2) is prepared in the range of 5×

10<sup>−

4</sup>˜

1×

10<sup>−

1</sup> moles for every 1 mole of active hydrogen compound;

under the conditions of reaction temperature 40˜

120°

C., maximum reaction pressure of 686 kPa (7 kgf/cm²), alkylene oxide is addition polymerized, and said crude polyoxyalkylene polyol is manufactured.