WO2001068602A1 - A new oligomer compound and a use thereof - Google Patents

A new oligomer compound and a use thereof Download PDF

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Publication number
WO2001068602A1
WO2001068602A1 PCT/SE2001/000511 SE0100511W WO0168602A1 WO 2001068602 A1 WO2001068602 A1 WO 2001068602A1 SE 0100511 W SE0100511 W SE 0100511W WO 0168602 A1 WO0168602 A1 WO 0168602A1
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WO
WIPO (PCT)
Prior art keywords
oligomer
polymerization
new
oligomer compound
desmodur
Prior art date
Application number
PCT/SE2001/000511
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French (fr)
Inventor
Jan Ericsson
Original Assignee
Perstorp Flooring Ab
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Perstorp Flooring Ab filed Critical Perstorp Flooring Ab
Priority to AU2001239631A priority Critical patent/AU2001239631A1/en
Publication of WO2001068602A1 publication Critical patent/WO2001068602A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D207/00Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06Esters of carbamic acids
    • C07C271/08Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/24Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring

Definitions

  • the present invention relates to a new oligomer compound having the formula
  • n is an integer between 2 and 6 inclusive.
  • Photoinitiator free means that no residual fragments from the initiator are left in the cured coating This is extremely important for outdoor stability and for mate ⁇ als in food contact
  • the coating becomes photobleached upon curing, which basically means that the remaining photoactivity within the cured coating is minimized This also means that thicker coatings can be cured more efficiently *
  • the adhesion can be expected to be optimized due to created covalent bonding between the coating and the coated surface. This is a consequence of the polymerization mechanism (curing) in charge transfer induced polymerization, where hydrogen abstraction is considerably involved. In particular, it is well known that hydrogens adjacent to heteroatoms like oxygen, nitrogen, etc. are easily abstracted. Consequently this is likely to take place if for example cellulose is included in the surface being coated by this polymerization process.
  • the polymerization may be carried out at any optional temperature, which is advantageous for applications on heat sensitive materials and surfaces (furniture, etc.).
  • the polymerization may be carried out locally through a mask (compare photoimaging).
  • the total polymerization time for this type of system is relatively fast, and is in the order of fractions of seconds up to minutes for total conversion of reactive groups.
  • the performance determining unit(s) which represents the main part of the molecular weight, gives the main contribution to the final mechanical properties of the cured coating. Improvements regarding abrasion, scratch and water resistance, and also improved gloss and finish in general can be obtained by surface coating modification by UV technology. The final properties of the surfaces will be given by the characters of the functional groups within the molecules and their distribution, molecular weight, flexibility, etc.
  • novel oligomer according to the present invention would work as a reactive component at the production of UV curable photoinitiator free lacquers and powder coatings.
  • a novel bis-maleimide oligomer according to one embodiment of the invention can be produced as schematically shown in fig. 1 below.
  • n 2-6, preferably 2.
  • a novel vinylether oligomer according to another embodiment of the invention can be produced as schematically shown in Fig. 2 below
  • n 2-6, preferably 2-4
  • the vinyl ether oligomer was obtained by mixing Desmodur® W and 2-hydroxyethyl vinyl ether in an organic solvent at catalytic conditions to form a vinyl ether oligomer called BIS-VE-DW below
  • BIS-VE-DW vinyl ether oligomer
  • Example 1 then relates to a reaction between Dosmodur® W and HEMI.
  • Example 2 illustrates a reaction between Desmodur® W and 2-hydroxyethyl vinyl ether.
  • Example 3 illustrates the use of the new oligomers of examples 1 and 2 as reactive components at the production of a UV curable photoinitiator free lacquer.
  • a 50/50 molar ratio mixture was prepared from BIS-MI-DW and BIS-VE-DW.
  • the polymerization proceeded efficiently without the addition of a photoinitiator system.
  • the products obtained were transparent and not discolored.
  • a new oligomer of the present invention can be combined with another complementary compound when used for UV curable photoinitiator free lacquers and/or powder coatings.

Abstract

A new oligomer compound of formula (I) where a) R is (II) or b) R is CH2 = CH - O - and where n is 2-6 and the use of the oligomer in UV curable lacquers and powder coatings.

Description

A NEW OLIGOMER COMPOUND AND A USE THEREOF
The present invention relates to a new oligomer compound having the formula
Figure imgf000002_0001
wherein R is A) or B) CH2=CH-O—
Figure imgf000002_0002
and wherein n is an integer between 2 and 6 inclusive. and the use of the oligomer as a reactive component at the production of UV-curable photoinitiator free lacquers and powder coatings.
Such a production has got an increasing importance and means a so-called charge transfer photoinduced co-polymeπzation of donor/acceptor combinations of monomers
These systems do not require the presence of a photoinitiator in order to initiate the polymerization process. Practically, the polymerization is induced by irradiation with UV light only, supplied by a high power lamp source. The basic requirement for the curing process to take place is that a suitable monomer/oligomer combination is present in the coating formulation. If such a combination consists of equal amounts of acceptor monomers (contains electron poor double bonds) together with donor monomers (contains electron πch double bonds), an efficient photopolymerization takes place.
There are several very attractive general characteristics connected with this new chemistry and among the most important are:
* The inhibition of oxygen in the polymerization process is minimized
* Photoinitiator free; means that no residual fragments from the initiator are left in the cured coating This is extremely important for outdoor stability and for mateπals in food contact
* The coating becomes photobleached upon curing, which basically means that the remaining photoactivity within the cured coating is minimized This also means that thicker coatings can be cured more efficiently * The adhesion can be expected to be optimized due to created covalent bonding between the coating and the coated surface. This is a consequence of the polymerization mechanism (curing) in charge transfer induced polymerization, where hydrogen abstraction is considerably involved. In particular, it is well known that hydrogens adjacent to heteroatoms like oxygen, nitrogen, etc. are easily abstracted. Consequently this is likely to take place if for example cellulose is included in the surface being coated by this polymerization process.
* Non-yellowing coatings can be obtained.
* The polymerization may be carried out at any optional temperature, which is advantageous for applications on heat sensitive materials and surfaces (furniture, etc.).
* The polymerization may be carried out locally through a mask (compare photoimaging).
* The total polymerization time for this type of system is relatively fast, and is in the order of fractions of seconds up to minutes for total conversion of reactive groups.
* The investment cost is considered to be rather low.
* The space occupied by the UV equipment is relatively at a minimum.
The performance determining unit(s), which represents the main part of the molecular weight, gives the main contribution to the final mechanical properties of the cured coating. Improvements regarding abrasion, scratch and water resistance, and also improved gloss and finish in general can be obtained by surface coating modification by UV technology. The final properties of the surfaces will be given by the characters of the functional groups within the molecules and their distribution, molecular weight, flexibility, etc.
It was quite surprising that the novel oligomer according to the present invention would work as a reactive component at the production of UV curable photoinitiator free lacquers and powder coatings.
A novel bis-maleimide oligomer according to one embodiment of the invention can be produced as schematically shown in fig. 1 below.
Fi___L
O [CH3(CH2)IoC 2]2Sn[(CH2)sCH2]2
OCN - -CH2- -NCO + 2 N — (CH2)nOH
O
Figure imgf000004_0001
where n is 2-6, preferably 2.
In one specific embodiment where n in above formula is 2, dicyclohexyl methane diisocyanate (Desmodur®W) was reacted with 2-hydroxyethylmaleιmιde (HEMI) in an organic solvent at catalytic conditions to form a novel bismaleimide oligomer called Bis-MI-DW below
HEMI can per se be produced according to our copending Swedish patent application
A novel vinylether oligomer according to another embodiment of the invention can be produced as schematically shown in Fig. 2 below
Fif l
[CH3(CH2),0OO2hSn[(CH2)3CH2]2
Figure imgf000004_0002
n is 2-6, preferably 2-4
In one specific embodiment where n in above formula is 2, the vinyl ether oligomer was obtained by mixing Desmodur® W and 2-hydroxyethyl vinyl ether in an organic solvent at catalytic conditions to form a vinyl ether oligomer called BIS-VE-DW below The invention is further illustrated by the embodiment examples 1-3 below of which example 1 then relates to a reaction between Dosmodur® W and HEMI. Example 2 illustrates a reaction between Desmodur® W and 2-hydroxyethyl vinyl ether. Example 3 illustrates the use of the new oligomers of examples 1 and 2 as reactive components at the production of a UV curable photoinitiator free lacquer.
Example 1
HEMI ( 5 g, 35.4 mmoles) was dissolved in acetone. The known catalyst shown on Fig. 1 was added and then dicyclohexylmethane diisocyanate (Desmodur® W) (4.45 g, 17 mmoles) was added dropwise at room temperature while stirring. The reaction mixture was then stirred over night. The acetone was evaporated and the remaining crude product was recrystallized from ethanol/acetone. The product was filtered and washed with ethanol and finally dried at vacuum. 'H NMR (CDC13) confirmed (Table 1 below) the pure bismaleimide (BIS-MI-DW) of Fig. 1 where n is 2. The yield was 4.6 g (50 % based on Desmodur W).
Table 1
Figure imgf000005_0001
Example 2
2-hydroxyethyl vinyl ether (3.2 g, 35.4 mmoles) was dissolved in acetone. The reaction mixture was treated under dry conditions for 2 hours. The known catalyst shown on Fig. 2 was added and then dicyclohexylmethane diisocyanate (Desmodur® W) (4.45 g, 17 mmoles) was added dropwise while stirring at room temperature. The reaction mixture was then stirred over night. The acetone was evaporated and the remaining crude product was recrystallized from ethanol/acetone. The product was filtered and washed with ethanol and finally dried at vacuum. 'H NMR (CDC13) confirmed (Table 2 below) the pure vinyl ether oligomer BIS-VE-DW of Fig. 2 where n is 2. The yield was 3.2 g (43 % based on Desmodur W). Table 2
Figure imgf000006_0001
Example 3
A 50/50 molar ratio mixture was prepared from BIS-MI-DW and BIS-VE-DW.
Typically 5 mg of this mixture was loaded into an aluminium DSC sample pan. The temperature of the sample was increased from 0°C to 130°C at a rate of 100°C/min. The polymerization temperature was 130°C and this temperature was kept for 15 s, 30 s and 45 s respectively and then the lamp source was turned on for 60 s. A slight decrease in the polymerization exotherms could be seen, which means that the polymerization continuously proceeded with time above the melting temperature without additional initiation by the UV source.
The polymerization proceeded efficiently without the addition of a photoinitiator system.
The products obtained were transparent and not discolored.
The invention is not limited to the embodiments shown since these can be modified in various ways within the scope of the invention. For instance a new oligomer of the present invention can be combined with another complementary compound when used for UV curable photoinitiator free lacquers and/or powder coatings.

Claims

A new oligomer compound having the formula
Figure imgf000007_0001
where a) R is
Figure imgf000007_0002
or b) R is CH2 = CH - O
and where n is 2-6
2. A compound according to claim 1, alternative a) where n is 2
3. A compound according to claim 1 alternative b) where n is 2-4.
4. Use of the compound according to any one of claims 1-3, as a reactive component in UV curable photoinitiator free lacquers and powder coatings.
PCT/SE2001/000511 2000-03-13 2001-03-12 A new oligomer compound and a use thereof WO2001068602A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001239631A AU2001239631A1 (en) 2000-03-13 2001-03-12 A new oligomer compound and a use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0000812A SE516275C2 (en) 2000-03-13 2000-03-13 New oligomer compound and use thereof
SE0000812-8 2000-03-13

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007030352A2 (en) 2005-09-07 2007-03-15 Transitions Optical, Inc. Photochromic multifocal optical article
US7811480B2 (en) 2004-03-04 2010-10-12 Transitions Optical, Inc. Photochromic optical article
CN103275249A (en) * 2013-05-24 2013-09-04 郑州大学 Free radical photoinitiator containing single vinyl ether group or single propenyl ether group, and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4217396A (en) * 1979-05-10 1980-08-12 Armstrong Cork Company Acrylate-acetoacetate polymers useful as protective agents for floor coverings
US4751273A (en) * 1986-08-19 1988-06-14 Allied-Signal, Inc. Vinyl ether terminated urethane resins
US5387367A (en) * 1990-11-20 1995-02-07 Basf Aktiengesellschaft Nonaqueous polyisocyanate formulation
EP0878482A1 (en) * 1997-05-16 1998-11-18 Dainippon Ink And Chemicals, Inc. An active energy ray curable composition comprised of a maleimide derivative and a method for curing the said curable composition
WO1999039247A1 (en) * 1998-01-30 1999-08-05 First Chemical Corporation Photopolymerization compositions including maleimides and processes for using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4217396A (en) * 1979-05-10 1980-08-12 Armstrong Cork Company Acrylate-acetoacetate polymers useful as protective agents for floor coverings
US4751273A (en) * 1986-08-19 1988-06-14 Allied-Signal, Inc. Vinyl ether terminated urethane resins
US5387367A (en) * 1990-11-20 1995-02-07 Basf Aktiengesellschaft Nonaqueous polyisocyanate formulation
EP0878482A1 (en) * 1997-05-16 1998-11-18 Dainippon Ink And Chemicals, Inc. An active energy ray curable composition comprised of a maleimide derivative and a method for curing the said curable composition
WO1999039247A1 (en) * 1998-01-30 1999-08-05 First Chemical Corporation Photopolymerization compositions including maleimides and processes for using the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7811480B2 (en) 2004-03-04 2010-10-12 Transitions Optical, Inc. Photochromic optical article
WO2007030352A2 (en) 2005-09-07 2007-03-15 Transitions Optical, Inc. Photochromic multifocal optical article
US7258437B2 (en) 2005-09-07 2007-08-21 Transitions Optical, Inc. Photochromic multifocal optical article
CN103275249A (en) * 2013-05-24 2013-09-04 郑州大学 Free radical photoinitiator containing single vinyl ether group or single propenyl ether group, and preparation method thereof

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SE0000812L (en) 2001-09-14
SE516275C2 (en) 2001-12-10
SE0000812D0 (en) 2000-03-13
AU2001239631A1 (en) 2001-09-24

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