CN102093549A - Catalyst for preparing polycarbonate polyol - Google Patents

Catalyst for preparing polycarbonate polyol Download PDF

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CN102093549A
CN102093549A CN2009103111791A CN200910311179A CN102093549A CN 102093549 A CN102093549 A CN 102093549A CN 2009103111791 A CN2009103111791 A CN 2009103111791A CN 200910311179 A CN200910311179 A CN 200910311179A CN 102093549 A CN102093549 A CN 102093549A
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talcums
bimetal
hydrotalcite
polycarbonate polyol
metal water
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王公应
王丽苹
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Changzhou Institute of Chemistry
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Changzhou Institute of Chemistry
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Abstract

The invention discloses a hydrotalcite-like catalyst for preparing polycarbonate polyol. The catalyst is special for an exchange reaction between an organic acidic carbonate and an aliphatic glycol ester to prepare the polycarbonate polyol. The structure of the catalyst accords with the following general formula: [M12+xM23+y(OH)2][An-](2x+3y-2)/n.mH2O, wherein the M12+ is one or two metals of the following divalent metals: magnesium, zinc, barium, calcium or copper; the M23+ is one of the following trivalent metals: aluminum or ferrum; the An- is a carbonate ion or a bicarbonate ion; the x is the mole number or the mole number sum of the M12+; the y is the mole number of the M23+; and the m is the number of water molecules. The catalyst provided by the invention is efficient and non-toxic, is low in using amount, is not required to be separated from the product after being used and does not affect the quality of the product. When the catalyst is used for preparing the polycarbonate polyol, the preparation process is simple and economical and the obtained product is high in quality.

Description

Preparation polycarbonate polyol catalyzer
Technical field
The invention belongs to catalysis technical field, relate in particular to the catalyzer that a kind of organic carbonate and binary aliphatic alcohol transesterification reaction prepare polycarbonate polyol.
Background technology
Polycarbonate polyol is that molecular end is all hydroxyl, and molecular backbone chain contains the polymkeric substance of alkylidene group and carbonate group repeating unit, is the important source material of producing polycarbonate polyurethane of new generation.Compare with the urethane that traditional polyvalent alcohol (polyester polyol, polyether glycol) is prepared, polycarbonate polyurethane by the polycarbonate polyol preparation has better thermotolerance, weathering resistance, water tolerance, germ resistance, scale resistance and mechanical property (Lee D K, Tai H B, Wang H H, etal.Joural of Applied Polymer Science, 2004, (94): 1723 ~ 1729).
Traditional phosgenation is produced polycarbonate polyol technology because of raw material phosgene severe toxicity, and a large amount of hydrogenchloride of by-product, and equipment is caused heavy corrosion, and is seriously polluted, is eliminated substantially.Non-phosgene is produced the extensive concern that polycarbonate polyol cleaning procedure such as cyclic carbonate ring-opening polymerization method, carbonic acid gas epoxide adjusting copolymerization method and carbonic ether and binary alcohol esters exchange process are subjected to industry.The synthetic cost of cyclic carbonate is higher, is difficult to generally promote in industrial production.Carbonic acid gas is a reserves rich in natural resources very on the earth, but the carbonic acid gas epoxide is regulated copolymerization method and can only be synthesized the polycarbonate polyol of specific epoxide structure.By adjusting the kind of dibasic alcohol, carbonic ether and binary alcohol esters exchange process can be synthesized the polycarbonate polyol with multiple structure, and the adjustability height of relative molecular weight, and product colourity is low, and the hydroxy functional group degree is relatively near theoretical value.Therefore, carbonic ether and binary alcohol esters exchange preparation polycarbonate polyol has become the focus of domestic and international research.
Under no catalytic condition, organic carbonate and dibasic alcohol can not react substantially, therefore must come accelerated reaction by means of catalyzer.At present, the catalyzer that is used for carbonic ether and binary alcohol esters exchange polycarbonate synthesis polyol reaction mainly contains sodium methylate (Wang Yutian, Tian Hengshui, Zhu Yunfeng, Liu Heng. urethane, 2008 (5): 78 ~ 80), sodium ethylate (Xie Xingyi, Li Jiehua, He Chengsheng, Fan Cuirong, the clock elecscreen. polymer material science and engineering, 2002,18 (4): 169 ~ 173), basic metal or alkaline-earth metal inorganic salt (Pitor Pawlowski, Gabriel Rokicki.Polymer, 2004, (45): 3125 ~ 3137), organo-tin compound (Chinese patent application number 02152740.7) also has III, IV, the organometallic compound of V family.The side reaction that the highly basic of sodium methylate, sodium ethylate causes is more, and deviates from thoroughly not to be easy to cause follow-up urethane and gel occurs when synthetic, if poor sealing when reducing pressure polycondensation in addition, easy oxidized variable color.The catalytic activity of basic metal or alkaline-earth metal inorganic salt is not very high.Organo-tin compound is the potential carcinogen in the human body, and catalytic activity neither be very high.Therefore seek that a kind of catalytic activity height, side reaction are few, the catalyzer of hypotoxicity and compliance with environmental protection requirements is key point
Summary of the invention
The object of the invention is to introduce a kind of catalytic activity height, few, the hypotoxic organic carbonate of side reaction and binary aliphatic alcohol transesterification reaction and prepares the polycarbonate polyol catalyzer.
For achieving the above object, the present invention proposes a kind of preparation polycarbonate polyol catalyzer, this catalyzer is exclusively used in the reaction that organic acid carbon ester and binary aliphatic alcohol transesterification reaction prepare polycarbonate polyol, and described catalyzer is bimetal houghite or three metal species hydrotalcites.
The structure of above-mentioned bimetal houghite such as general formula I:
[M 1 2+ xM 3 3+ y(OH) 2][A n-] (2x+3y-2)/n·mH 2O…………………I
M wherein 1Be a kind of metallic element in divalence magnesium, zinc, barium, calcium or the copper.
M 3Be a kind of metallic element in trivalent aluminium or the iron;
A N-Be carbanion or bicarbonate ion, i.e. A N-N=2 during for carbanion, A N-N=1 during for bicarbonate ion;
X is M 1 2+Mole number, y is M 2 3+Mole number;
M is the number of water molecules.
The ratio of x in the above-mentioned general formula I: y is between 2: 1 ~ 4: 1.
Above-mentioned bimetal houghite catalyzer is Mg-Al bimetal hydrotalcite or Ca-Al bimetal hydrotalcite or Zn-Al bimetal hydrotalcite or Cu-Al bimetal hydrotalcite or Ni-Al bimetal hydrotalcite or Ba-Al bimetal hydrotalcite or Mg-Fe bimetal hydrotalcite or Ca-Fe bimetal hydrotalcite or Zn-Fe bimetal hydrotalcite or Cu-Fe bimetal hydrotalcite or Ni-Fe bimetal hydrotalcite or Ba-Fe bimetal hydrotalcite.
The structure of above-mentioned three metal species hydrotalcites such as general formula I I:
[M 1 2+ aM 2 2+ bM 3 3+ y(OH) 2][A n-] (2(a+b)+3y-2)/n·mH 2O………II
M wherein 1And M 2Be respectively two kinds of different metal elements in divalence magnesium, zinc, barium, calcium or the copper.
M 3Be a kind of metallic element in trivalent aluminium or the iron;
A N-Be carbanion or bicarbonate ion, i.e. A N-N=2 during for carbanion, A N-N=1 during for bicarbonate ion;
A is M 1 2+Mole number, b is M 2 2+Mole number, y is M 2 3+Mole number;
M is the number of water molecules.
The ratio of (a+b): y is between 2: 1 ~ 4: 1 among the above-mentioned general formula I I.
Above-mentioned three metal species hydrotalcite catalysts are Mg-Zn-Al three metal water talcums or Mg-Cu-Al three metal water talcums or Mg-Ba-Al three metal water talcums or Mg-Ca-Al three metal water talcums or Zn-Cu-Al three metal water talcums or Zn-Ba-Al three metal water talcums or Zn-Ca-Al three metal water talcums or Cu-Ba-Al three metal water talcums or Cu-Ca-Al three metal water talcums or Ba-Ca-Al three metal water talcums or Mg-Zn-Fe three metal water talcums or Mg-Cu-Fe three metal water talcums or Mg-Ba-Fe three metal water talcums or Mg-Ca-Fe three metal water talcums or Zn-Cu-Fe three metal water talcums or Zn-Ba-Fe three metal water talcums or Zn-Ca-Fe three metal water talcums.
Above-mentioned bimetal hydrotalcite catalyst or three metal water talcum catalyst consumption are 0.005% ~ 1.0% of reactant quality.
Above-mentioned organic carbonate can be selected from methylcarbonate, diethyl carbonate, NSC 11801, diphenyl carbonate any one; Described aliphatic dihydroxy alcohol can be selected from 1,4-butyleneglycol, 1,3 butylene glycol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexylene glycol any one or two kinds.
The mol ratio of above-mentioned aliphatic dihydroxy alcohol and organic carbonate is between 1.06 ~ 2.0.
Above-mentioned method for preparing catalyst: by x: y=2: 1 ~ 4: 1 feed ratio is dissolved in divalent metal nitrate makes solution I in the deionized water; A certain amount of trivalent metal nitrate is dissolved in solution II in the deionized water; Sodium hydroxide and yellow soda ash (or sodium bicarbonate) is dissolved in the deionized water to pH value between 8 ~ 10, makes solution III.Solution I and II are injected into solution III simultaneously, 60 ℃ of following heated and stirred 2 hours, again 60 ℃ of following ageings 10 hours, suction filtration, washing, 100 ℃ of dryings 18 hours are made 20 ~ 40 order particles, obtain the lamellar compound hydrotalcite.
The present invention has following characteristics:
(1) the preparation polycarbonate polyol of this proposition of the present invention is active high with catalyst, and the by product yield is more than 60%; Nontoxicity can coexist with product, the color and luster unanimity, not needing increases and the product separation steps, and the product quality is not had influence, can satisfy environmental protection requirement, can guarantee active requirement again, so the present invention is the catalyzer of new and effective preparation polycarbonate polyol.
(2) the catalyzer source of the present invention's proposition is wide, easily obtains, and preparation is simple, and consumption is few, and is with low cost.
Embodiment
Embodiment 1
With 15.00g1,4-butyleneglycol, 30.00g diphenyl carbonate, 0.0301g Mg 3Al (OH) 2(HCO 3) 73H 2O bimetal hydrotalcite catalyst joins in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feeds air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 4.0 hours.Then, system pressure is reduced to 3.6 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 4.5 * 10 gradually 3Pa keeps 6h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 7.5h, obtains the 6.81g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 68.8%, and the viscosity-average molecular weight of PCDL is 1602.5.
Embodiment 2
With 20.00g1,3-butyleneglycol, 30.00g diphenyl carbonate, 0.0150gZn 3Al (OH) 2(HCO 3) 75H 2O bimetal hydrotalcite catalyst joins in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feeds air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 2.5 hours.Then, system pressure is reduced to 4.0 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 5.2 * 10 gradually 3Pa keeps 4h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 8.85g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 76.8%, and the viscosity-average molecular weight of PCDL is 2302.5.
Embodiment 3
With 18.00g1,5-pentanediol, 30.00g diphenyl carbonate, 0.0152g Mg 2ZnAl (OH) 2(HCO 3) 712H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.0 hours.Then, system pressure is reduced to 3.6 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 6.5 * 10 gradually 3Pa keeps 8h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 7.94g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 65.1%, and the viscosity-average molecular weight of PCDL is 2002.5.
Embodiment 4
With 20.00g1,6-hexylene glycol, 30.00g diphenyl carbonate, 0.0151g Mg 3Zn 3Al 2(OH) 2(HCO 3) 1620H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.5 hours.Then, system pressure is reduced to 4.6 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 5.5 * 10 gradually 3Pa keeps 5h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 7.21g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 72.8%, and the viscosity-average molecular weight of PCDL is 1962.9.
Embodiment 5
With 20.00g1,6-hexylene glycol, 30.00g diphenyl carbonate, 0.0152g CaZn 2Al (OH) 2(HCO 3) 710H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.5 hours.Then, system pressure is reduced to 5.0 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 4.5 * 10 gradually 3Pa keeps 7h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 5.36g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 62.8%, and the viscosity-average molecular weight of PCDL is 1302.5.
Embodiment 6
With 20.00g1,6-hexylene glycol, 30.00g diphenyl carbonate, 0.0150g Ca 3Al (OH) 2(HCO 3) 710H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.0 hours.Then, system pressure is reduced to 4.2 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 6.5 * 10 gradually 3Pa keeps 6h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 5.71g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 70.8%, and the viscosity-average molecular weight of PCDL is 1902.5.
Embodiment 7
With 20.00g1,4-hexylene glycol, 30.00g diphenyl carbonate, 0.0151g Ba 3Al (OH) 2(HCO 3) 78H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 4.0 hours.Then, system pressure is reduced to 5.2 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 5.1 * 10 gradually 3Pa keeps 7h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 6.15g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 59.8%, and the viscosity-average molecular weight of PCDL is 1202.7.
Embodiment 8
With 15.00g1,4-butyleneglycol, 30.00g diphenyl carbonate, 0.0301g Mg 3Fe 2(OH) 2(CO 3) 53H 2O bimetal hydrotalcite catalyst joins in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feeds air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 4.0 hours.Then, system pressure is reduced to 3.6 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 4.5 * 10 gradually 3Pa keeps 6h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 7.5h, obtains the 4.81g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 38.8%, and the viscosity-average molecular weight of PCDL is 502.5.
Embodiment 9
With 10.00g1,3-butyleneglycol, 10.00g1,6-hexylene glycol, 30.00g diphenyl carbonate, 0.0150gZn 3Al 2(OH) 2(CO 3) 55H 2O bimetal hydrotalcite catalyst joins in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feeds air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 2.5 hours.Then, system pressure is reduced to 4.0 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 5.2 * 10 gradually 3Pa keeps 4h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 8.85g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 74.8%, and the viscosity-average molecular weight of PCDL is 2202.5.
Embodiment 10
With 18.00g1,5-pentanediol, 30.00g diphenyl carbonate, 0.0152g Mg 2Zn 2Fe 2(OH) 2(CO 3) 612H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.0 hours.Then, system pressure is reduced to 3.6 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 6.5 * 10 gradually 3Pa keeps 8h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 4.94g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 45.1%, and the viscosity-average molecular weight of PCDL is 572.5.
Embodiment 11
With 20.00g1,6-hexylene glycol, 30.00g diphenyl carbonate, 0.0151g Mg 3Cu 3Al 2(OH) 2(CO 3) 820H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.5 hours.Then, system pressure is reduced to 4.6 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 5.5 * 10 gradually 3Pa keeps 5h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 5.21g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 52.8%, and the viscosity-average molecular weight of PCDL is 762.9.
Embodiment 12
With 20.00g1,6-hexylene glycol, 30.00g diphenyl carbonate, 0.0152g CuZn 2Al 2(OH) 2(CO 3) 510H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.5 hours.Then, system pressure is reduced to 5.0 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 4.5 * 10 gradually 3Pa keeps 7h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 5.86g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 60.8%, and the viscosity-average molecular weight of PCDL is 1002.5.
Embodiment 13
With 20.00g1,6-hexylene glycol, 30.00g diphenyl carbonate, 0.0150g Cu 3Al 2(OH) 2(CO 3) 510H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 3.0 hours.Then, system pressure is reduced to 4.2 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 6.5 * 10 gradually 3Pa keeps 6h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 5.71g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 68.8%, and the viscosity-average molecular weight of PCDL is 1612.5.
Embodiment 14
With 10.00g1,4-hexylene glycol, 10g1,5-pentanediol, 30.00g diphenyl carbonate, 0.0151gBa 4Fe 2(OH) 2(CO 3) 68H 2O three metal hydrotalcite catalysts join in the 100mL round-bottomed flask that thermometer, nitrogen conduit, mechanical stirring and rectifying column are housed, and feed air in the nitrogen replacement reactor.Under the normal pressure system temperature is risen to 192 ~ 206 ℃, control fractional column temperature is 180 ℃, in time fractionates out by-product phenol, back flow reaction 4.0 hours.Then, system pressure is reduced to 5.2 * 10 gradually 4Pa, reaction 2h.Carrying out along with reaction reduces system pressure to 5.1 * 10 gradually 3Pa keeps 7h.Product dissolves with methylene dichloride, ethanol sedimentation, and washing, suction filtration in 48 ℃ of following vacuum-drying 8h, obtains the 6.15g polycarbonate polyol.The phenol yield in synthesis under normal pressure stage is 39.8%, and the viscosity-average molecular weight of PCDL is 402.7.

Claims (10)

1. one kind prepares the polycarbonate polyol catalyzer, it is characterized in that: this catalyzer is exclusively used in the reaction that organic acid carbon ester and binary aliphatic alcohol transesterification reaction prepare polycarbonate polyol, and described catalyzer is bimetal houghite or three metal species hydrotalcites.
2. a kind of preparation polycarbonate polyol catalyzer according to claim 1 is characterized in that: the structure of described bimetal houghite such as general formula I:
[M12xM33y(OH)2][An-](2x+3y-2)/n·mH2O…………………I
Wherein M1 is a kind of metallic element in divalence magnesium, zinc, barium, calcium or the copper.
M3 is a kind of metallic element in trivalent aluminium or the iron;
An-is carbanion or bicarbonate ion, n=2 when promptly An-is carbanion, n=1 when An-is bicarbonate ion;
X is the mole number of M12, and y is the mole number of M23;
M is the number of water molecules.
3. a kind of preparation polycarbonate polyol catalyzer according to claim 2, it is characterized in that: the ratio of x in the described general formula I: y is between 2: 1 ~ 4: 1.
4. a kind of preparation polycarbonate polyol catalyzer according to claim 3 is characterized in that: described bimetal houghite catalyzer is Mg-Al bimetal hydrotalcite or Ca-Al bimetal hydrotalcite or Zn-Al bimetal hydrotalcite or Cu-Al bimetal hydrotalcite or Ni-Al bimetal hydrotalcite or Ba-Al bimetal hydrotalcite or Mg-Fe bimetal hydrotalcite or Ca-Fe bimetal hydrotalcite or Zn-Fe bimetal hydrotalcite or Cu-Fe bimetal hydrotalcite or Ni-Fe bimetal hydrotalcite or Ba-Fe bimetal hydrotalcite.
5. a kind of preparation polycarbonate polyol catalyzer according to claim 1 is characterized in that: the structure of described three metal species hydrotalcites such as general formula I I:
[M12aM22bM33y(OH)2][An-](2(a+b)+3y-2)/n·mH2O………II
Wherein M1 and M2 are respectively two kinds of different metal elements in divalence magnesium, zinc, barium, calcium or the copper.
M3 is a kind of metallic element in trivalent aluminium or the iron;
An-is carbanion or bicarbonate ion, n=2 when promptly An-is carbanion, n=1 when An-is bicarbonate ion;
A is the mole number of M12, and b is the mole number of M22, and y is the mole number of M23;
M is the number of water molecules.
6. a kind of preparation polycarbonate polyol catalyzer according to claim 5, it is characterized in that: the ratio of (a+b): y is between 2: 1 ~ 4: 1 among the described general formula I I.
7. a kind of polycarbonate polyol catalyst for preparing according to claim 6, it is characterized in that: described three metal species hydrotalcite catalysts are Mg-Zn-Al three metal water talcums or Mg-Cu-Al three metal water talcums or Mg-Ba-Al three metal water talcums or Mg-Ca-Al three metal water talcums or Zn-Cu-Al three metal water talcums or Zn-Ba-Al three metal water talcums or Zn-Ca-Al three metal water talcums or Cu-Ba-Al three metal water talcums or Cu-Ca-Al three metal water talcums or Ba-Ca-Al three metal water talcums or Mg-Zn-Fe three metal water talcums or Mg-Cu-Fe three metal water talcums or Mg-Ba-Fe three metal water talcums or Mg-Ca-Fe three metal water talcums or Zn-Cu-Fe three metal water talcums or Zn-Ba-Fe three metal water talcums or Zn-Ca-Fe three metal water talcums.
8. according to claim 4 or 7 described a kind of preparation polycarbonate polyol catalyzer, it is characterized in that: described bimetal hydrotalcite catalyst or three metal water talcum catalyst consumption are 0.005% ~ 1.0% of reactant quality.
9. a kind of preparation polycarbonate polyol catalyzer according to claim 1 is characterized in that: described organic carbonate can be selected from methylcarbonate, diethyl carbonate, NSC 11801, diphenyl carbonate any one; Described aliphatic dihydroxy alcohol can be selected from 1,4-butyleneglycol, 1,3 butylene glycol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexylene glycol any one or two kinds.
10. a kind of preparation polycarbonate polyol catalyzer according to claim 9, it is characterized in that: the mol ratio of described aliphatic dihydroxy alcohol and organic carbonate is between 1.06 ~ 2.0.
CN2009103111791A 2009-12-10 2009-12-10 Catalyst for preparing polycarbonate polyol Pending CN102093549A (en)

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CN109369392A (en) * 2018-11-02 2019-02-22 安徽工程大学 A kind of synthetic method of two carbonic ester of the dimethyl of straight chain containing ether-oxygen bond
CN111234196A (en) * 2020-03-20 2020-06-05 东莞市左镕工实业有限公司 Polycarbonate resin for elastic hand feeling paint, preparation method thereof and elastic hand feeling paint

Cited By (6)

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CN103447020A (en) * 2013-09-13 2013-12-18 上海大学 Composite metal oxide catalyst for preparing biodiesel
CN106179174A (en) * 2016-07-07 2016-12-07 同济大学 For layered composite metal hydroxides removing water pollutant and its preparation method and application
CN106179174B (en) * 2016-07-07 2019-04-12 同济大学 Layered composite metal hydroxides and its preparation method and application for removing water pollutant
CN109369392A (en) * 2018-11-02 2019-02-22 安徽工程大学 A kind of synthetic method of two carbonic ester of the dimethyl of straight chain containing ether-oxygen bond
CN109369392B (en) * 2018-11-02 2021-11-23 安徽工程大学 Synthesis method of ether oxygen bond-containing straight-chain dimethyl dicarbonate
CN111234196A (en) * 2020-03-20 2020-06-05 东莞市左镕工实业有限公司 Polycarbonate resin for elastic hand feeling paint, preparation method thereof and elastic hand feeling paint

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Application publication date: 20110615