CN107365408A - Castor oil based polyurethanes resin and its making - Google Patents
Castor oil based polyurethanes resin and its making Download PDFInfo
- Publication number
- CN107365408A CN107365408A CN201710797055.3A CN201710797055A CN107365408A CN 107365408 A CN107365408 A CN 107365408A CN 201710797055 A CN201710797055 A CN 201710797055A CN 107365408 A CN107365408 A CN 107365408A
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- CN
- China
- Prior art keywords
- castor oil
- resin
- based polyurethanes
- oil based
- isocyanate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Castor oil based polyurethanes resin and its making, using pure castor oil, polymerisation in bulk directly is carried out with two isocyanate groups, aggregates into hydroxy-end capped castor oil based polyurethanes resin.The making of castor oil based polyurethanes resin of the present invention：It uses not chemically treated pure castor oil, with the calculation of mol ratio, allows the Liang Ge functional groups in castor oil to aggregate into the hydroxy-end capped castor oil based polyurethanes resin of branched straight chain type structure with two isocyanate groups；Change the molecular weight of this resin, just obtain：Sticky uncured fluidised form, not flowable uncured colloid, a series of castor oil based polyurethanes resin of the different performances of polyurethane resin solidified.On raw material, the dosage of castor oil accounts for 70-80%, according to the difference of molecular weight product, the dosage of adjustment castor oil and two isocyanate groups, you can obtain the product that performance differs greatly.The present invention is based on living resources castor oil, energy-saving and environmental protection.
Description
Technical field
The present invention relates to castor oil based polyurethanes resin and its making.
Background technology
Castor oil is than more rich living resources, and its Polarity comparision is small, with the polyurethane water-proof paint that it is synthesized,
Water resistance and compliance are good, should largely be used in architectural waterproof material.However, the polyurethane waterproof material with castor oil-base
It is seldom.Reason is that mostly at present used after castor oil either is carried out into the chemical treatment such as alcoholysis to castor oil in a solvent,
Not only cost had been increased but also had polluted environment, so eliminating substantially.
Current water-repellent paint, all it is to be coated on waterproof basal plane the waterproof after its film-forming.If waterproof basal plane
It is concrete surface, when concrete surface is broken, the water-repellent paint that is coated on concrete surface is also dragged therewith to be split, and is lost anti-
Water effect.Existing water-repellent paint, waterproof foamed glue, water-proof emulsion, although also doing raw material with point castor oil sometimes, castor oil
Dosage it is considerably less, fossil resource it is more.
The existing high polymer waterproof material overwhelming majority is all fossil resource, and this is not meet energy-saving and environmental protection, reduce
Carbon row, reduce cost, and the industrial policy of sustainable development.Why not past is built with polyurethane based on castor oil resin
Waterproof material, it is because this resin viscosity and cohesive force are all very big, the one-component of pure matter uses highly difficult.Two-component uses,
Although also there is a two-component irrigation sprinkler in the past, the component proportion difference very little of A, B two, usually 1:1, preferably at most 2:1, it is not suitable for castor
Sesame oil based polyurethanes resin uses.The content of the invention
The purpose of the present invention, is to provide for a kind of castor oil based polyurethanes resin and its making, and polyurethane based on castor oil resin is used
When water-repellent paint is done, it is non-curing type, and it will not be broken because of the fracture of concrete surface, can conversely be healed automatically disconnected
Crack.By changing molecular weight product, the castor oil based polyurethanes resin of different shape is produced, it is different with the existing field boundary of reply construction
Situation.For example product made sticky uncured fluid by 1., water-repellent paint, this water-repellent paint and conventional waterproof coating can be done
Compare, remain the waterproof advantage of " flawless ", while add again and be not broken and be broken with concrete surface, can be with self-healing
Close crack, can be with self-closed concrete surface pore the advantages of.2. product is made into not flowable uncured colloid, it is
Low modulus elastomer, available for building expansion joint and the waterproof of concrete surface faulted joint, it can be used as pressure sensitive adhesive, marine glue
Band uses.3. product to be made to the castor oil based polyurethanes resin of solidification, closed available for the waterproof field boundary for needing to solidify, such as need to be with mixing
Solidifying soil solidifies integral structure.It can use the irrigation sprinkler that adjustable two-component matches, i.e. two components are matched up to 10：1
Two-component irrigation sprinkler, matched by adjusting two-component, it is possible to above-mentioned three kinds of products of spraying, or multiple product, to use castor-oil plant
Oil base polyurethane resin creates condition.
The thinking source of the present invention is the isocyanates of pure castor oil and two degrees of functionality, or has two isocyanate groups
Performed polymer, carry out bulk polymerization.Castor oil is the glyceryl ester and the two of 30% castor oil acidic groups of 70% castor oil acid
With an oleic acid base or the mixture of the glyceryl ester of linoleic acid base.Therefore, about 70% oleic acid is three-functionality-degree, 30%
Oleic acid be two degrees of functionality, i.e., average functionality be 2.7.In design, two functions in 2.7 functional groups of castor oil are only allowed
Group generates the hydroxy-end capped castor oil based polyurethanes resin of branched straight chain type structure with two isocyanate groups.Change this tree
The molecular weight of fat, it is possible to which the castor oil base for obtaining the multiple performances such as sticky uncured fluidised form, semisolid, pseudo-solid condition, solid-state gathers
Urethane resin.
The present invention is achieved in that the castor oil based polyurethanes resin, using pure castor oil, directly with two isocyanic acids
Base carries out polymerisation in bulk, aggregates into hydroxy-end capped castor oil based polyurethanes resin.
The making of castor oil based polyurethanes resin of the present invention：It uses not chemically treated pure castor oil,
With the calculation of mol ratio, the Liang Ge functional groups allowed in castor oil aggregate into branched straight chain type structure with two isocyanate groups
Hydroxy-end capped castor oil based polyurethanes resin；Change the molecular weight of this resin, just obtain：Sticky uncured fluidised form, no
The castor oil based polyurethanes resin of flowable uncured colloid, a series of different performances of polyurethane resin solidified.
The calculation of mol ratio of the present invention is, N moles of castor oil with（N-1）Mole two isocyanate groups are gathered
Close, molecular weight after polymerization for N moles of castor oil+（N-1）Mole two isocyanate groups；The castor oil based polyurethanes of one ton of production
Resin, with 1000 divided by polymerization after molecular weight, then with the mutually multiplied castor oil charged material weight of N moles of castor oil, with（N-1）
Mole mutually multiplied two isocyanate groups charged material weight of two isocyanate groups.
The invention has the advantages that on raw material, the dosage of castor oil accounts for 70-80%, according to molecular weight product
Difference, adjust the dosages of castor oil and two isocyanate groups, you can obtain the castor oil based polyurethanes resin that performance differs greatly.
The present invention energy-saving and environmental protection, reduces carbon emission, production cost is low based on living resources castor oil.
Embodiment
The mol ratio computational methods that feed intake of the present invention are as follows：
Because castor oil is mixture, the molecular weight of every batch of castor oil is not exclusively the same, it is necessary to be determined after chemical examination.It is typically
900-1000 or so.Castor oil molecule amount=1000 are currently assumed for convenience of description.If want to make a kind of molecular weight for one
Ten thousand or so hydroxy-end capped polyurethane based on castor oil resin, can set the castor oil with 8 moles（That is N=8）, rubbed with 7
You（That is N-1）'-diphenylmethane diisocyanate（MT）It is polymerize.MT molecular weight=250.Molecular weight=8 after polymerization ×
1000+7 × 250=8000+1750=9750.It is assumed that thinking the polyurethane based on castor oil resin of about 1 ton or so of production, just use
800kg castor oil is polymerize with 175kg MT.
If mole N=20 of castor oil,（N-1）Individual mole, MT=19, the polyurethane based on castor oil resin after polymerization
Molecular weight=20 × 1000+19 × 250=20000+4750=24750.If also keep within bounds 1 ton or so of castor oil-base to gather
Urethane resin, castor oil still use 800kg, MT=800/20000 × 4750=190kg.
If mole N=100 of castor oil,（N-1）Individual mole, MT=99, the polyurethane based on castor oil resin after polymerization
Molecular weight=100 × 1000+99 × 250=100000+24750=124750.If also keep within bounds 1 ton or so of castor oil
Based polyurethanes resin, castor oil still use 800kg, MT=800/100000 × 24750=198kg.
The molecular weight of polyurethane based on castor oil resin is very big by 9750-24750-124750, the change of molecular weight.Work as castor oil
When being all 800kg, MT 175kg-190kg-198kg, MT weight change very little.This just illustrates, when poor for 10 with proportioning:1
Two-component irrigation sprinkler when, fixed castor oil component, few micro-adjustment once MT amount is very big with regard to that can adjust out mass difference,
The polyurethane based on castor oil resin that namely performance differs greatly, the castor oil-base of multiple functions requirement can be provided for buildings waterproof
Polyurethane resin.
The embodiment of the present invention is as follows：
1st, one-component polyurethane based on castor oil resin water-repellent paint is produced.
Castor oil is first dehydrated and gone the removal of impurity.Feed intake design calculate when, by N number of mole of castor oil with（N-1）Individual mole
Two isocyanate groups are reacted.N size is depending on the performance requirement to waterproof material.It is assumed that the molecular weight of this batch of castor oil
=1000, if with pure '-diphenylmethane diisocyanate（MT）It is polymerize with castor oil, then MT molecular weight=250.If
Think the polyurethane based on castor oil resin of 10000 or so molecular weight of production, N=8, N-1=7 can be selected.The castor oil-base of design gathers
Molecular weight=8 of urethane resin × 1000+7 × 250=8000+1750=9750, castor oil and MT ingredients by weight ratio, just
It is 8000:1750, if it is desired to do 1 ton or so of polyurethane based on castor oil resin, then it can use 800kg castor oil and 175kg
MT is reacted.The molecular structure of this proportioning, in theory namely branched straight chain type structure.Because castor oil has 2.7
Individual functional group, what is reacted is the isocyanates of two functional groups, and castor oil can only have two functional groups to react, other
0.7 functional group reformed into side chain.
One-component is only suitable for low viscosity, and at a certain temperature, heating can be thinning, is suitable for one-component sprinkling irrigation, or
The occasion of manual application.The resin of this low viscosity, general molecular weight is smaller, about 6000-10000 or so.First by two groups
The molecular weight that raw material needs according to waterproof, accurately calculate the weight of each group.Castor oil component is all first added into reaction vessel,
Start agitating device.70 DEG C or so are warming up to, is then gradually added two isocyanate group components again.Raised according to viscosity, suitably carried
High-temperature, but do not exceed 110 DEG C.About react two hours and discharge, or discharge in advance, also may proceed to react after discharging.
2nd, polyurethane based on castor oil resin water-repellent paint is produced with two-component irrigation sprinkler.
Will be after physical treatment or go back the castor oil of adding assistant as component A, the component A for being added to irrigation sprinkler is held
In device, and it is preheating to 70 DEG C；By two isocyanate group components, as B component, it is added in the B component container of irrigation sprinkler, also preheats
To 70 DEG C.Then according to the production capacity of irrigation sprinkler, and the molecular weight of the polyurethane resin required for waterproof, calculate A, B two
The theoretical weight ratio of component, and set the respective weight of two components respectively on irrigation sprinkler, then start irrigation sprinkler.In A, B
Before two components do not mix, within the same time, the component of A, B two is taken out respectively, and is weighed respectively, carried out pair with theoretical value
Than.Adjust repeatedly, until equal with theory.Even the two is equal, yet by two components of taking-up in appropriate containers
Middle heating response, see whether result is close with waterproof requirement.After having done these preparations, you can sprinkling irrigation construction.If it is desired to
Change the function of polyurethane based on castor oil resin, as long as somewhat adjusting B component, so that it may meet to require.
Polyurethane based on castor oil resin of the present invention, with the change of molecular weight, there are many excellent characteristics, can use
In the occasion of a variety of buildings waterproofs, such as uncured water-repellent paint, the waterproof at expansion joint, the leak stopping of concrete crack, and adhesive waterproof tape
Deng.
According to《Chemical industry dictionary》Definition to " resin " is " the amorphous organic matter of semisolid, solid-state or pseudo-solid condition
Matter "；When fusing " heated to soften, and gradually melt, tacky "；" it can be divided into according to source：Natural resin, synthetic resin, artificial tree
Fat ".The present invention is that pure castor oil carries out polymerisation in bulk, " synthetic resin " of generation with diisocyanate.And this synthesis tree
Fat, it is according to mol ratio（Without equivalent proportion）Computational methods, it is aggregated into branched straight chain structure and hydroxy-end capped
Polyurethane based on castor oil resin.The ratio of castor oil used in this structure, according to the difference of molecular weight, castor oil dosage accounts for
70%-80%. and cohesive force is stronger, elasticity is also more preferable, and this is that do not had in the past.Carried out with pure castor oil and two isocyanate groups
Polymerisation in bulk, it is for environmentally friendly and multi-purpose living resources；Calculated with the method for mol ratio, be to generate branched straight chain type
Structure, cross-linked structure is avoided as far as possible；Hydroxy-end capped is for the more difficult solidification of low-molecular-weight resin.
Claims (3)
1. castor oil based polyurethanes resin, it is characterized in that：Pure castor oil, polymerisation in bulk, polymerization are directly carried out with two isocyanate groups
Into hydroxy-end capped castor oil based polyurethanes resin.
2. the making of castor oil based polyurethanes resin described in claim 1：It is characterized in that：It is not using chemically treated
Pure castor oil, with the calculation of mol ratio, the Liang Ge functional groups in castor oil are allowed to be aggregated into two isocyanate groups branched
The hydroxy-end capped castor oil based polyurethanes resin of straight chain type structure；Change the molecular weight of this resin, just obtain：It is sticky non-solid
Change fluidised form, not flowable uncured colloid, a series of castor oil based polyurethanes tree of the different performances of polyurethane resin solidified
Fat.
3. the making of castor oil based polyurethanes resin according to claim 2, it is characterized in that：The calculation of the mol ratio
For, N moles of castor oil with（N-1）Mole two isocyanate groups are polymerize, the molecular weight after polymerization be N moles of castor oil+（N-
1）Mole two isocyanate groups；The castor oil based polyurethanes resin of one ton of production, with the molecular weight behind 1000 divided by polymerization, Ran Houyu
The mutually multiplied castor oil charged material weight of N moles of castor oil, with（N-1）Mole mutually multiplied two isocyanate group of two isocyanate groups feeds intake weight
Amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710797055.3A CN107365408A (en) | 2017-09-06 | 2017-09-06 | Castor oil based polyurethanes resin and its making |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710797055.3A CN107365408A (en) | 2017-09-06 | 2017-09-06 | Castor oil based polyurethanes resin and its making |
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| CN107365408A true CN107365408A (en) | 2017-11-21 |
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| CN201710797055.3A Pending CN107365408A (en) | 2017-09-06 | 2017-09-06 | Castor oil based polyurethanes resin and its making |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020015276A1 (en) * | 2018-07-17 | 2020-01-23 | 四川大学 | Injectable polyurethane and manufacturing method therefor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125545A (en) * | 1976-07-19 | 1978-11-14 | N L Industries, Inc. | Stabilized diphenylmethane diisocyanate prepolymer |
| US4877829A (en) * | 1988-05-19 | 1989-10-31 | W. R. Grace & Co.-Conn. | Liquid coatings for bridge deckings and the like |
| US5290632A (en) * | 1992-05-01 | 1994-03-01 | W. R. Grace & Co.-Conn. | Liquid coatings for cast iron |
| CN101831048A (en) * | 2010-05-05 | 2010-09-15 | 嘉兴市罗星化工有限公司 | High-gloss polyurethane resins and application thereof |
| CN102140327A (en) * | 2011-02-28 | 2011-08-03 | 中国科学院宁波材料技术与工程研究所 | Storable plant oil-based polyurethane wood adhesive and preparation method and application thereof |
| CN102417779A (en) * | 2011-08-11 | 2012-04-18 | 湖北蓝盾之星科技股份有限公司 | Preparation process of bicomponent castor oil polyurethane waterproof coating |
| CN102532465A (en) * | 2012-02-21 | 2012-07-04 | 中国科学院长春应用化学研究所 | Preparation method for hyperbranched polyurethane, modified polylactic resin, and preparation method for modified polylactic resin |
| CN104327236A (en) * | 2014-10-23 | 2015-02-04 | 盐城工学院 | Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof |
-
2017
- 2017-09-06 CN CN201710797055.3A patent/CN107365408A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125545A (en) * | 1976-07-19 | 1978-11-14 | N L Industries, Inc. | Stabilized diphenylmethane diisocyanate prepolymer |
| US4877829A (en) * | 1988-05-19 | 1989-10-31 | W. R. Grace & Co.-Conn. | Liquid coatings for bridge deckings and the like |
| US5290632A (en) * | 1992-05-01 | 1994-03-01 | W. R. Grace & Co.-Conn. | Liquid coatings for cast iron |
| CN101831048A (en) * | 2010-05-05 | 2010-09-15 | 嘉兴市罗星化工有限公司 | High-gloss polyurethane resins and application thereof |
| CN102140327A (en) * | 2011-02-28 | 2011-08-03 | 中国科学院宁波材料技术与工程研究所 | Storable plant oil-based polyurethane wood adhesive and preparation method and application thereof |
| CN102417779A (en) * | 2011-08-11 | 2012-04-18 | 湖北蓝盾之星科技股份有限公司 | Preparation process of bicomponent castor oil polyurethane waterproof coating |
| CN102532465A (en) * | 2012-02-21 | 2012-07-04 | 中国科学院长春应用化学研究所 | Preparation method for hyperbranched polyurethane, modified polylactic resin, and preparation method for modified polylactic resin |
| CN104327236A (en) * | 2014-10-23 | 2015-02-04 | 盐城工学院 | Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020015276A1 (en) * | 2018-07-17 | 2020-01-23 | 四川大学 | Injectable polyurethane and manufacturing method therefor |
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