CN1869100A - Preparation method of high molecular weight polyaspartic acid - Google Patents
Preparation method of high molecular weight polyaspartic acid Download PDFInfo
- Publication number
- CN1869100A CN1869100A CN200610085649.3A CN200610085649A CN1869100A CN 1869100 A CN1869100 A CN 1869100A CN 200610085649 A CN200610085649 A CN 200610085649A CN 1869100 A CN1869100 A CN 1869100A
- Authority
- CN
- China
- Prior art keywords
- acid
- polyaspartic acid
- high molecular
- aspartic acid
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 25
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 8
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000005227 gel permeation chromatography Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 2
- 239000000498 cooling water Substances 0.000 abstract description 2
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000003337 fertilizer Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000008635 plant growth Effects 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 229960005261 aspartic acid Drugs 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 4
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003672 gas field water Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a preparation method of polyaspartic acid with high molecular weight, which is characterized by comprising the following steps: adding catalyst into aspartic acid as raw material and mixing; and (3) polycondensation reaction: the temperature is 160-240 ℃, the vacuum degree is 0.08-0.09 MPa, and the time is 1-2 hours; grinding, and sieving with 100 mesh sieve; repeating the second step and the third step; washing with water to neutrality; drying at 80 ℃ under normal pressure for 2 hours, wherein the weight average molecular mass of the obtained polyaspartic acid is 20000-200000. The advantages are that: the polyaspartic acid is a polyamino acid with a carboxylic acid side chain, and is a safe, non-toxic and harmless completely biodegradable high molecular compound. The polyaspartic acid is an excellent scale inhibition and dispersion agent and is used for water treatment of circulating cooling water systems, boilers and oil and gas fields; the polyaspartic acid is used as a fertilizer synergist and can promote plant growth; excellent moisture retention performance, and is used for manufacturing daily cosmetics and health care products; the polyaspartic acid can be used for preparing super absorbent resin and oil field viscosity reducer.
Description
Technical field
That the present invention relates to is the preparation method of a kind of poly aspartic acid (PASP), relates in particular to the preparation that is used for oil field viscosity-depression agent and the required high molecular weight polyasparagic acid of water-absorbing resin.Belong to the poly aspartic acid technical field.
Technical background
The preparation method of poly aspartic acid, there is patent report can adopt aspartic acid monomer direct polymerization, also have patent report to adopt maleic acid or its ammonium salt directly synthetic, but the molecular weight of these method institute synthetic poly aspartic acids is less, the purposes of product is restricted.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with the aspartic acid, the method for preparing high molecular weight polyasparagic acid, with the aspartic acid is raw material, add catalyzer, at a certain temperature, the vacuum polycondensation generates poly aspartic acid, it is pulverized, repolymerization repeats this process, the poly aspartic acid of the son amount that can secure satisfactory grades.This method technological process is simple, and the big I of molecular weight is realized control, and end-use is wide.
Technical solution of the present invention: the preparation method of high molecular weight polyasparagic acid, it is characterized in that processing step divides one, proportioning raw materials: with the aspartic acid is raw material, add catalyst mix, described catalyzer is phosphoric acid, polyphosphoric acid, sulfuric acid, and the mass ratio of aspartic acid and catalyzer is 5～2: 1; Two, polycondensation: the temperature of polycondensation is 160～240 ℃, and polycondensation is carried out under vacuum tightness 0.08～0.09Mpa condition, reaction times 1-2 hour; Three, pulverize,
Cross 100 mesh sieves; Four, repeating step two, three, determine multiplicity according to the size of desired molecule amount; Five, be washed to neutrality; Six, 80 ℃ of constant pressure and dries are 2 hours, and the weight average molecular mass of gained poly aspartic acid is 20000～200000.
Advantage of the present invention: the mentioned poly aspartic acid of the present invention is a kind of polyamino acid that has carboxylic acid side chain, is safe, nontoxic, fully biodegradable, environment amenable macromolecular compound.Poly aspartic acid is a kind of good dirt dispersion agent, is used for recirculating cooling water system, boiler and oil-gas field water treatment; Poly aspartic acid as fertilizer sources synergistic agent can promote plant-growth; It also has good performance of keeping humidity, is used for the manufacturing of daily cosmetics and health-care product; Can prepare High hydrophilous resin and oil field viscosity-depression agent by poly aspartic acid.
Embodiment
Embodiment 1:
In the 1000ml beaker, add L-aspartic acid 50g, phosphoric acid 25g is after stirring, put into vacuum drying oven, control reaction temperature is 180 ℃, carries out polycondensation under the vacuum tightness 0.088MPa condition, after 2h is carried out in reaction, reactant is taken out, pulverize, cross 100 mesh sieves, continue reaction again.After 1h is carried out in reaction, material is taken out, pulverizes, crosses 100 mesh sieves, continue reaction.Repeat said process once.Product water is washed till neutrality; 80 ℃ of constant pressure and dries 2 hours.
Measured the average weight-molecular mass (M of poly aspartic acid with gel chromatography (GPC)
W).Gel column is TSK GMPWXL 7.8 * 300, and moving phase is 0.05M Na
2SO
4, flow velocity is 0.5ml/min, is standard specimen with the polyacrylic acid.GPC records the M of this product
WBe 23000.
Embodiment 2:
In the 1000ml beaker, add L-aspartic acid 50g, phosphoric acid 20g is after stirring, put into vacuum drying oven, control reaction temperature is 200 ℃, carries out polycondensation under the vacuum tightness 0.09MPa condition, after reaction is carried out 2 hours, reactant is taken out, pulverize, cross 100 mesh sieves, continue reaction again.After 1 hour, material is taken out, pulverizes, crosses 100 mesh sieves, continue reaction.Repeat said process eight times.Product water is washed till neutrality; 80 ℃ of constant pressure and dries 2 hours.Measured the average weight-molecular mass (M of poly aspartic acid with gel chromatography (GPC)
W) be 185000.
Embodiment 3:
In the 1000ml beaker, add L-aspartic acid 50g, phosphatase 11 2.5g is after stirring, put into vacuum drying oven, control reaction temperature is 220 ℃, carries out polycondensation under the vacuum tightness 0.09MPa condition, after reaction is carried out 2 hours, reactant is taken out, pulverize, cross 100 mesh sieves, continue reaction again.After reaction is carried out 1 hour, material is taken out, pulverizes, crosses 100 mesh sieves, continue reaction.Repeat said process three times.Product water is washed till neutrality, 80 ℃ of constant pressure and dries 2 hours.Measured the average weight-molecular mass (M of poly aspartic acid with gel chromatography (GPC)
W) be 112000.
Embodiment 4:
In the 1000ml beaker, add L-aspartic acid 40g, polyphosphoric acid 12g, after stirring, put into vacuum drying oven, control reaction temperature is 180 ℃, carries out polycondensation under the vacuum tightness 0.09MPa condition, after reaction is carried out 2 hours, reactant is taken out, pulverize, continue reaction 4 hours again, product water is washed till neutrality, 80 ℃ of constant pressure and dries 2 hours.Measured the average weight-molecular mass (M of poly aspartic acid with gel chromatography (GPC)
W) be 36000.
Claims (3)
1, the preparation method of high molecular weight polyasparagic acid, it is characterized in that processing step divides one, proportioning raw materials: with the aspartic acid is raw material, add catalyst mix, described catalyzer is phosphoric acid, polyphosphoric acid, sulfuric acid, and the mass ratio of aspartic acid and catalyzer is 5～2: 1; Two, polycondensation: the temperature of polycondensation is 160～240 ℃, and polycondensation is carried out under vacuum tightness 0.08～0.09Mpa condition, reaction times 1-2 hour; Three, pulverize, cross 100 mesh sieves; Four, repeating step two, three, determine multiplicity according to the size of desired molecule amount; Five, be washed to neutrality; Six, 80 ℃ of constant pressure and dries are 2 hours, and the weight average molecular mass of gained poly aspartic acid is 20000～200000.
2, the preparation method of high molecular weight polyasparagic acid according to claim 1 is characterized in that determining that according to the size of desired molecule amount multiplicity is 1-8 time.
3, the preparation method of high molecular weight polyasparagic acid according to claim 1 is characterized in that measuring the average weight-molecular mass (M of poly aspartic acid
w) usefulness gel chromatography (GPC).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610085649.3A CN1869100A (en) | 2006-06-28 | 2006-06-28 | Preparation method of high molecular weight polyaspartic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610085649.3A CN1869100A (en) | 2006-06-28 | 2006-06-28 | Preparation method of high molecular weight polyaspartic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1869100A true CN1869100A (en) | 2006-11-29 |
Family
ID=37442890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610085649.3A Pending CN1869100A (en) | 2006-06-28 | 2006-06-28 | Preparation method of high molecular weight polyaspartic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1869100A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643543B (en) * | 2009-09-07 | 2011-07-06 | 石家庄开发区德赛化工有限公司 | Prepration method of special polyaspartic acid for agriculture |
| CN110330956A (en) * | 2019-07-10 | 2019-10-15 | 黑龙江益瑞化工有限公司 | A kind of Environment-protecting Drilling Fluids polyaminoacid class thinner and preparation method thereof |
| CN115785440A (en) * | 2022-11-01 | 2023-03-14 | 罗恒 | Preparation method of biodegradable polyaspartic acid and application of biodegradable polyaspartic acid in fertilizer synergist |
-
2006
- 2006-06-28 CN CN200610085649.3A patent/CN1869100A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643543B (en) * | 2009-09-07 | 2011-07-06 | 石家庄开发区德赛化工有限公司 | Prepration method of special polyaspartic acid for agriculture |
| CN110330956A (en) * | 2019-07-10 | 2019-10-15 | 黑龙江益瑞化工有限公司 | A kind of Environment-protecting Drilling Fluids polyaminoacid class thinner and preparation method thereof |
| CN110330956B (en) * | 2019-07-10 | 2020-07-03 | 黑龙江益瑞化工有限公司 | Environment-friendly polyamino acid viscosity reducer for drilling fluid and preparation method thereof |
| CN115785440A (en) * | 2022-11-01 | 2023-03-14 | 罗恒 | Preparation method of biodegradable polyaspartic acid and application of biodegradable polyaspartic acid in fertilizer synergist |
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