CN108084056A - A kind of block copolymerization type carbodiimides and preparation method thereof - Google Patents
A kind of block copolymerization type carbodiimides and preparation method thereof Download PDFInfo
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- CN108084056A CN108084056A CN201711498010.2A CN201711498010A CN108084056A CN 108084056 A CN108084056 A CN 108084056A CN 201711498010 A CN201711498010 A CN 201711498010A CN 108084056 A CN108084056 A CN 108084056A
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- Prior art keywords
- carbodiimides
- block copolymerization
- diisocyanate
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- alicyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to a kind of block copolymerization type carbodiimides, have following general structure：
Description
Technical field
The present invention relates to carbodiimides and preparation method thereof more particularly to a kind of block copolymerization type carbonizations two
Imine compound and preparation method thereof.
Background technology
China is agricultural production big country, and to the use of mulch since 1979, current area coverage has reached 3.7 hundred million
Mu, annual output reaches 1,310,000 tons within 2012, it is contemplated that area coverage in 2017 be up to 4.5 hundred million mu, yield be up to 1,500,000 tons.
The common ground film used at present, about 25% or so remains in the soil after annual use.
These remaining mulches are made mostly of polyethylene raw material, without any degradation property, it is difficult to recycle, and recycle
Economic value is low, can remain 100 years or more in the soil.As the residual quantity that non-degradable mulch is accumulated is increasing, to soil
And endangering also increasing caused by crops, mulch residue problem has become the ecological problem of social concerns at present.
The residual of mulch is reduced or eliminated except encouraging to recycle residual film, mainly greatly develops the full biology drop of popularization by government
Solve plastic film.The industrialization at present and raw material that can be used for biodegradable plastic mulch has：Polylactic acid (PLA), polycyclic oxygen
Propane-carbon dioxide copolymer (PPC) and poly-succinic-terephthalic acid (TPA)-butanediol ester (PBAT) etc..Biodegradable mulch exists
Carbon dioxide and water can be slowly decomposed by the microorganisms into soil, will not be damaged to environment, crops will not be influenced
Yield, be a kind of very environmentally protective material, have sustainable developability.
In the past 10 years, it is ever-expanding using center to have carried out scale throughout the country for the agricultural technology extension of the Ministry of Agriculture of China
Trying out for Biodegradable mulch, has been achieved for gratifying success.But it integrates, Biodegradable mulch is at present in use
Also there are the main problems such as low, fast, the water conservation difference of degradation of pulling force.
The acid value for reducing biodegradation material is the key that solve the problems, such as.The acid value of material is lower, and stability is better, then drops
Solution rate is slower, and application cost can also reduce.The major way for improving Biodegradable mulch stability in use at present is that addition is anti-
Hydrolytic reagent.
Carbodiimides are a kind of excellent stabilisers against hydrolysis, and the high molecular material containing ester group is by water or acid
During erosion, the ester bond in molecule is cracked into alcohol and acid, and acid can be such that hydrolysis rate exponentially rises again, Carbodiimides
Compound can capture this free carboxy acid, the stable uride of fast reaction generation under room temperature, prevent hydrolysis further deeply, from
And improve the hydrolytic stability of high molecular material.
Carbodiimides include single second carbide imine, more carbodiimides, polycarbodiimide class compound.
Single second carbide imine sexual valence is higher, and effect is the most superior in all carbodiimides, but due to its molecule
It measures relatively low, not only easily volatilizees and decompose in processing, smell is larger；Also there can be the risk of migration in follow-up use.
The fusing point of aggretion type carbodiimides is relatively high or infusibilized, and aggretion type carbodiimides includes two major classes at present：
(1) aromatic series polymerization carbodiimides, it is typical as Rhein is chemical
La Xige companiesDeng；(2) aliphatic or alicyclic polymerization carbodiimides, it is typical such as Nisshinbo
HMV-8CA, LA-1 of company etc..
Aromatic series polymerization Carbodiimide reaction activity is relatively low, and color is more yellow, it is difficult to inhibit in process, polyester
The degradation of material.And aliphatic or alicyclic polymerization carbodiimides have higher reactivity, but when in use, easily
The viscosity of material system is caused to explode, material is caused to be difficult to or formed fisheye, in thin film fabrication, can cause rupture of membranes or
Other visual defects.
The content of the invention
The carbodiimides that the present invention designs is on the basis of aggretion type carbodiimides, by block copolymerization, by two
The oligomer of kind of carbodiimides aggregates into the carbodiimides of more macromolecule by chain extending reaction.It ensure that carbonization two
The resistant to hydrolysis long-term effect of imines, but energy work in-process quickly reduces the content of carboxyl end group of system, and greatly reduce material system
Viscosity rise.
One of the objects of the present invention is to provide a kind of novel blocks to be copolymerized carbodiimides.
The second object of the present invention is the preparation method for providing the block copolymerization carbodiimides.
A kind of block copolymerization carbodiimides have following general structure：
Wherein, Ar is aryl compound, and A is the aliphatic of C2~C20 or alicyclic hydrocarbon compound；A1For C2~C20
Hydrocarbon compound, Y1、Y2For amino-formate bond, urea bond or amido bond, n, n ' be 1~8 integer.
The block copolymerization carbodiimides are prepared by following methods：
1) in inert gas environment, aromatic diisocyanate acts under high temperature (140~200 DEG C) through catalyst 1
It is condensed into aromatic series carbodiimides oligomer.
2) in inert gas environment, aliphatic or alicyclic diisocyanate urging through catalyst 1 at 140~200 DEG C
Aliphatic or alicyclic carbodiimides oligomer is prepared in change effect condensation.After cooling to 100~150 DEG C, chain extension is added in
Agent occurs end capping reaction and obtains intermediate product.Aromatic series carbodiimides oligomer is added in intermediate product, at 140~200 DEG C
1~2h is reacted through catalyst 2, obtains block copolymerization carbodiimides.
One or more mixtures of the inert gas in nitrogen, helium, neon, argon gas, carbon dioxide.
The aromatic diisocyanate includes triisopropyl phenylene diisocyanate, toluene di-isocyanate(TDI) (TDI), hexichol
Dicyclohexylmethane diisocyanate (MDI), 4,4 '-di-2-ethylhexylphosphine oxide (2,6- diisopropyls) phenylisocyanate, two isocyanide of dimethyl diphenyl
Acid esters (TODI).
The aliphatic or alicyclic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate
(HDI), ten dimethylene diisocyanates, Isosorbide-5-Nitrae-diisocyanate root trimethylcyclohexane, trimethylhexane diisocyanate, 2,2- are double
(4- isocyanatocyclohexyls)-propane, isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methyl hydride diisocyanate
Double (2- isocyanato- -2- propyl) benzene (TMXDI), preferably 4,4'-Dicyclohexylmethane diisocyanate of ester (HMDI), 1,3-
(HMDI), double (2- isocyanato- -2- propyl) benzene (TMXDI) of 1,3-.
The catalyst 1 is organic phosphorus compound, selected from Phospholes, Phospholes oxide, diethoxy phosphinylidyne
Sulphur choline, diethoxyphosphinylthiocholine oxide and its mixture of two or more.It is preferred that by 1- methyl -2- phosphorus heterocycles
Amylene -1- oxides (MPPO) form.The additive amount of catalyst 1 is the 0.05%~0.3% of diisocyanate.
The catalyst 2 includes organometallic catalysts, such as organotin；It is and other as DBU, imidazoles are catalyzed
Agent, morpholine class catalyst etc..2 additive amount of catalyst is the 0.1%~1% of diisocyanate.
The chain extender is the small-molecule substance of double reactive groups, as one end is amino, one end is the small of hydroxyl or carboxyl
Molecular compound.Likewise, every have two different groups, can be reacted with isocyanate groups, and two groups
The different compound of reaction rate, can also be used as the chain extender of selection, and such group includes：Amino, hydroxyl, carboxyl, acid anhydrides
Group, epoxide group etc..The micromolecular compound that preferably one end is amino, one end is hydroxyl.For example：2- ethylaminoethanols, 1-
Amino -3- propyl alcohol etc..The chain extender is 1.1-1.2 with aliphatic or alicyclic diisocyanate molar ratio:1.
Step 2) the aliphatic or alicyclic carbodiimides oligomeric segment and step 1) aromatic series carbodiimides
The mass ratio of oligomeric segment is 0.1~10:1.
Step 2) the block copolymerization carbodiimides number-average molecular weight is 1000~20000, preferably 1500
~5000.
Gained block copolymerization carbodiimides of the invention can be used as stabilisers against hydrolysis, chain extender and add
Work auxiliary agent is for polyesters, polyamide compound, the especially biodegradations such as photovoltaic industry specialty films polyester material, mulch
Material, automobile using polyamide material etc. not only can effectively prevent the hydrolysis of polyester material, while compared to traditional haplotype
With aggretion type carbodiimides, the guarantee material that block copolymerization carbodiimides not only can be long-acting is in wet heat condition
Under performance, while the degradation of plastics in process can be inhibited significantly.
Description of the drawings：
Fig. 1：Fig. 1 is the carbon spectrogram of the block copolymerization carbodiimides synthesized by embodiment 1.
Fig. 2：Fig. 2 is the PLA and blank PLA for the block copolymerization carbodiimides that addition embodiment 1 synthesizes
Melt flow index test chart.
Fig. 3：Fig. 3 is to add block copolymerization carbodiimides and the commercially available resistant to hydrolysis that embodiment 1 synthesizes respectively
The acid value test chart of the polyester polyol of agent product SJ.
Specific implementation method：
Embodiment 1
1) in nitrogen protective atmosphere encloses, addition 8.58kg triisopropyl phenylene diisocyanates, 0.0429kg catalyst MPPO,
Polycondensation reaction, the poly- triisopropylbenzene carbodiimides that the obtained degree of polymerization is about 2 are carried out at 180 DEG C or so.
2) in nitrogen protective atmosphere encloses, by 10.48kg4,4 '-dicyclohexyl methyl hydride diisocyanate, 0.0524kg catalysis
Agent MMPO carries out polycondensation reactions at 160 DEG C, and the obtained degree of polymerization is about poly- the 4 of 3,4 '-dicyclohexyl methyl hydride carbodiimides.It will
The reaction is cooled to 120 DEG C, and in molar ratio 1.2:1 adds in chain extender 1- amino -3- propyl alcohol 0.9kg, reacts 1h, completes half and blocks
Intermediate product is obtained, poly- triisopropylbenzene carbodiimides is added in intermediate product, adds in the stannous octoate catalysis of 0.008kg
Agent is warming up to 140 DEG C, and 15.6kg white powder products are obtained after reacting 1.5h, is block copolymerization carbodiimides.
The carbon spectrogram of the product is as shown in Figure 1.
Applicating evaluating is made to the block copolymerization carbodiimides synthesized by embodiment 1：
The block copolymerization carbodiimides that 2.0phr embodiments 1 synthesize are made an addition into PLA, extruding pelletization, with
PLA 65 DEG C of boiling experiments simultaneously of auxiliary agent, test PLA melting means variations are not added, and the experimental data of Fig. 2 shows that adding block is total to
The PLA melt flow index of polycarbodiimide class compound is significantly lower than the PLA for not adding auxiliary agent.
The block copolymerization carbodiimides that embodiment 1 synthesizes are used for together with commercially available anti-hydrolysis agent product SJ
Polyester polyol deacidification value test experiments, Fig. 3's statistics indicate that, compared with commercially available anti-hydrolysis agent product SJ, block copolymerization carbonization
Diimine class compound can more effectively reduce polyester polyol acid value.
Claims (9)
1. a kind of block copolymerization type carbodiimides have following general structure：
Wherein, Ar is aryl compound, and A is the aliphatic of C2~C20 or alicyclic hydrocarbon compound；A1For the hydro carbons of C2~C20
Compound, Y1、Y2For amino-formate bond, urea bond or amido bond, n, n ' be 1~8 integer.
2. a kind of method for preparing block copolymerization type carbodiimides described in claim 1, comprises the following steps：
1) in inert gas environment, aromatic diisocyanate is acted on through catalyst 1 under high temperature (140~200 DEG C) and is condensed
Into aromatic series carbodiimides oligomer.
2) in inert gas environment, the catalysis work of aliphatic or alicyclic diisocyanate through catalyst 1 at 140~200 DEG C
Aliphatic or alicyclic carbodiimides oligomer is prepared with condensation.After being transferred to 100~150 DEG C, chain extender is added in, is occurred
End capping reaction obtains intermediate product.Aromatic series carbodiimides oligomer is added in intermediate product, through catalysis at 140~200 DEG C
1~2h is reacted in agent 2, obtains block copolymerization carbodiimides.
。
3. a kind of method for preparing block copolymerization type carbodiimides according to claim 2, the step
1) it is nitrogen with the inert gas of step 2), one or more mixtures in helium, neon, argon gas, carbon dioxide.
4. a kind of method for preparing block copolymerization type carbodiimides according to claim 2, the step
1) aromatic diisocyanate includes triisopropyl phenylene diisocyanate, toluene di-isocyanate(TDI), diphenylmethane diisocyanate
Ester, 4,4 '-di-2-ethylhexylphosphine oxide (2,6- diisopropyls) phenylisocyanate, dimethyl diphenyl diisocyanate.
5. a kind of method for preparing block copolymerization type carbodiimides according to claim 2, the fat
It is different that race or alicyclic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, ten dimethylenes two
Double (the 4- isocyanato- hexamethylenes of cyanate, Isosorbide-5-Nitrae-diisocyanate root trimethylcyclohexane, trimethylhexane diisocyanate, 2,2-
Base)-propane, isophorone diisocyanate, 4,4'-Dicyclohexylmethane diisocyanate, 1,3- it is double (2- isocyanato-s-
2- propyl) benzene.
6. a kind of method for preparing block copolymerization type carbodiimides according to claim 2, step (2) institute
Chain extender is stated as the small-molecule substance containing wherein 2 groups of amino, hydroxyl, carboxyl, anhydride group, epoxide group.
7. a kind of method for preparing block copolymerization type carbodiimides according to claim 2, step (2) institute
It is 1.1~1.2 that chain extender, which is stated, with aliphatic or alicyclic diisocyanate molar ratio:1.
8. a kind of method for preparing block copolymerization type carbodiimides according to claim 2, step 2) institute
State the quality of aliphatic or alicyclic carbodiimides oligomeric segment and step 1) aromatic series carbodiimides oligomeric segment
Than for 0.1~10:1.
9. a kind of method for preparing block copolymerization type carbodiimides according to claim 2, step 2) institute
Block copolymerization carbodiimides number-average molecular weight is stated as 1000~20000.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920359A (en) * | 2021-01-22 | 2021-06-08 | 上海涵点科技有限公司 | Synthesis method and application of copolymerization type polycarbodiimide |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08208788A (en) * | 1995-01-31 | 1996-08-13 | Mitsui Toatsu Chem Inc | Polycarbodiimide copolymer and production thereof |
| CN1245175A (en) * | 1998-07-01 | 2000-02-23 | 巴斯福公司 | Polycarbided diimine polymer and its use as inter-layer of adhesive layer in automobile paint |
| CN1055939C (en) * | 1993-06-11 | 2000-08-30 | 罗姆和哈斯公司 | Aromatic polycarbodiimide crosslinkers |
| US20010037010A1 (en) * | 2000-03-29 | 2001-11-01 | Heiko Tebbe | Polycarbodiimide-based block copolymers, a method of preparing them and their use as hydrolysis stabilizers |
| JP2002187932A (en) * | 2000-12-19 | 2002-07-05 | Dainichiseika Color & Chem Mfg Co Ltd | Polycarbodiimide compound, method for manufacturing the same and treating method of matter |
| CN1699438A (en) * | 2004-05-21 | 2005-11-23 | 日清纺织株式会社 | Thermosetting polycarbodiimide copolymer |
| JP2010260001A (en) * | 2009-05-07 | 2010-11-18 | Nippon Paint Co Ltd | Method of forming multilayered coating film |
| CN105940052A (en) * | 2014-02-05 | 2016-09-14 | 日清纺化学株式会社 | Polyester-based resin composition, production method for said polyester-based resin composition, and molded article using said polyester-based resin composition |
-
2017
- 2017-12-29 CN CN201711498010.2A patent/CN108084056A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055939C (en) * | 1993-06-11 | 2000-08-30 | 罗姆和哈斯公司 | Aromatic polycarbodiimide crosslinkers |
| JPH08208788A (en) * | 1995-01-31 | 1996-08-13 | Mitsui Toatsu Chem Inc | Polycarbodiimide copolymer and production thereof |
| CN1245175A (en) * | 1998-07-01 | 2000-02-23 | 巴斯福公司 | Polycarbided diimine polymer and its use as inter-layer of adhesive layer in automobile paint |
| US20010037010A1 (en) * | 2000-03-29 | 2001-11-01 | Heiko Tebbe | Polycarbodiimide-based block copolymers, a method of preparing them and their use as hydrolysis stabilizers |
| JP2002187932A (en) * | 2000-12-19 | 2002-07-05 | Dainichiseika Color & Chem Mfg Co Ltd | Polycarbodiimide compound, method for manufacturing the same and treating method of matter |
| CN1699438A (en) * | 2004-05-21 | 2005-11-23 | 日清纺织株式会社 | Thermosetting polycarbodiimide copolymer |
| JP2010260001A (en) * | 2009-05-07 | 2010-11-18 | Nippon Paint Co Ltd | Method of forming multilayered coating film |
| CN105940052A (en) * | 2014-02-05 | 2016-09-14 | 日清纺化学株式会社 | Polyester-based resin composition, production method for said polyester-based resin composition, and molded article using said polyester-based resin composition |
Non-Patent Citations (1)
| Title |
|---|
| 王北海: "四甲基苯二甲基二异氰酸酯专利(上) ", 《聚氨酯》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920359A (en) * | 2021-01-22 | 2021-06-08 | 上海涵点科技有限公司 | Synthesis method and application of copolymerization type polycarbodiimide |
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Application publication date: 20180529 |