(19)
(11)EP 3 121 206 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
10.06.2020 Bulletin 2020/24

(21)Application number: 16186410.3

(22)Date of filing:  13.11.2013
(51)International Patent Classification (IPC): 
C08F 226/02(2006.01)
C09D 139/00(2006.01)

(54)

NITROFUNCTIONAL ACRYLATE COPOLYMERS FOR BINDER COMPOSITIONS

NITROFUNKTIONELLE ACRYLAT-COPOLYMERE FÜR BINDEMITTELZUSAMMENSETZUNGEN

COPOLYMÈRES D'ACRYLATE À FONCTION NITRO POUR DES COMPOSITIONS DE LIANT


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 13.12.2012 US 201261736746 P

(43)Date of publication of application:
25.01.2017 Bulletin 2017/04

(62)Application number of the earlier application in accordance with Art. 76 EPC:
13799154.3 / 2931768

(73)Proprietor: ANGUS Chemical Company
Buffalo Grove, IL 60089 (US)

(72)Inventors:
  • BRUTTO, Patrick E.
    Bloomingdale, IL 60108 (US)
  • GREEN, George D.
    Cary, IL 60013 (US)
  • FU, Zhenwen
    Collegeville, PA (US)
  • GREYSON, Eric
    Blue Bell, PA 19422 (US)
  • HEJL, Andrew
    Landsdale, PA 19446 (US)
  • TANG, Jia
    Shanghai, 200438 (US)

(74)Representative: Harrison IP Limited 
3 Ebor House Millfield Lane
Nether Poppleton, York YO26 6QY
Nether Poppleton, York YO26 6QY (GB)


(56)References cited: : 
  
  • TAKAHASHI, KUNIHIRO ET AL: "The polymerization and copolymerization of nitroalkyl acrylates and nitroalkyl methacrylates", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 12, no. 7, 1968, pages 1683-1695, XP002718437, ISSN: 0021-8995, DOI: 10.1002/APP.1968.070120717
  • TANAKA, ATSUSHI ET AL: "Polymerization of nitroalkyl acrylates", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 8, no. 4, 1964, pages 1787-1799, XP002718438, ISSN: 0021-8995, DOI: 10.1002/APP.1964.070080428
  • DATABASE REGISTRY [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 16 November 1984 (1984-11-16), "CN- 2-Propenoic acid, 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl ester (CA INDEX NAME). OTHER CA INDEX NAMES:CN - Acrylic acid, 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl ester (8CI)", XP002721927, Database accession no. RN 21808-93-5
  • STRUMZA, J. ET AL: "Michael reaction with nitroform and related syntheses", ISRAEL JOURNAL OF CHEMISTRY , 1(2), 106-14 CODEN: ISJCAT; ISSN: 0021-2148, 1963, XP002767212, DOI: 10.1002/IJCH.196300020
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Cross-Reference to Related Applications



[0001] This application claims priority from provisional application serial number 61/736,746, filed December 13, 2012.

Field



[0002] This invention relates to nitrofunctional acrylate polymers which are for use in aqueous based paints and coatings and other applications.

Background



[0003] Paint and coating formulations are ubiquitous in today's societies. They are used on a wide variety of surfaces, for instance, metal, wood, plastics, brick, wallboard, etc., and for many functions, such as surface protection from chemical and/or physical hazards, for decoration, waterproofing, and the like.

[0004] Paints and coatings are typically composed of a binder material, a carrier or solvent, together with various other additives. The other additives may include, for instance, neutralizers, antimicrobials, pigments, uv absorbers, etc. The binders provide a network in which the other additives are dispersed and suspended. Binders also function as the primary film forming component of the finished coating, provide integrity and adhesion for the coated film and overall protect the substrate from the external environment. Generally, there are two classes of binders: latex binders, which are used in aqueous based formulations, and alkyd-based binders, which are used in non-aqueous formulations, ultimately resulting in latex paints and coatings and alkyd paints and coatings, respectively.

[0005] Aqueous based paints and coatings use water as the main carrier instead of an organic solvent. As a result, they are generally lower volatile organic content (VOC) materials and are therefore favored in some applications and regions where low VOC is desired or required. Aqueous based paints and coatings, however, may not provide the equivalent properties to their alkyd based counterparts. For instance, they may not provide equivalent protection against chemical or physical hazards, or as good adhesion to the substrate. Consequently, a continuing need exists to discover ways for improving the properties of aqueous based paints and coatings.

[0006] The problem addressed by this invention is the provision of binder compositions for use, for example, in aqueous based paints and coatings that provide improved properties over previous systems including, for instance, improved hardness and/or chemical resistance.

Statement of Invention



[0007] We have now found that the functionalization of acrylate polymers with nitro groups improves various properties of the polymer. Advantageously, when the nitrofunctional polyacrylate is used as a binder in an aqueous based paint or coating or other formulations, the formulation may exhibit better hardness, chemical resistance, or both. The formulation may also result in improved gloss.

[0008] The present inventors have developed a copolymer formed from one or more esters or amides of acrylic acid or methacrylic acid, or their mixtures, together with a monomer unit of formula I:



[0009] In one aspect of the present invention, there is provided a copolymer comprising a polymerized compound of 2-methyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 3-hydroxy-2-methyl-2-nitropropyl acrylate; 3-hydroxy-2-methyl-2-nitropropyl methacrylate; 2-ethyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-(hydroxymethyl)-2-nitrobutyl acrylate; 2-(hydroxymethyl)-2-nitrobutyl methacrylate; 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl methacrylate; 2-((methacryloyloxy)methyl)-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-methyl-2-nitrobutyl acrylate; 2-methyl-2-nitrobutyl methacrylate; N-(2-methyl-2-nitropropyl)methacrylamide; N,N-bis(2-methyl-2-nitropropyl)acrylamide; N,N-bis(2-methyl-2-nitropropyl)methacrylamide; N-isopropyl-N-(2-nitrobutyl)acrylamide; or N-isopropyl-N-(2-nitrobutyl)methacrylamide.

[0010] In another aspect, there is provided a compound that is: 2-methyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 3-hydroxy-2-methyl-2-nitropropyl acrylate; 3-hydroxy-2-methyl-2-nitropropyl methacrylate; 2-ethyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-(hydroxymethyl)-2-nitrobutyl acrylate; 2-(hydroxymethyl)-2-nitrobutyl methacrylate; 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl methacrylate; 2-((methacryloyloxy)methyl)-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-methyl-2-nitrobutyl acrylate; 2-methyl-2-nitrobutyl methacrylate; N-(2-methyl-2-nitropropyl)methacrylamide; N,N-bis(2-methyl-2-nitropropyl)acrylamide; N,N-bis(2-methyl-2-nitropropyl)methacrylamide; N-isopropyl-N-(2-nitrobutyl)acrylamide; or N-isopropyl-N-(2-nitrobutyl)methacrylamide.

Detailed Description



[0011] Unless otherwise indicated, numeric ranges, for instance as in "from 2 to 10," are inclusive of the numbers defining the range (e.g., 2 and 10).

[0012] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.

[0013] "Alkyl," as used in this specification, encompasses straight and branched chain aliphatic groups having the indicated number of carbon atoms. Preferred alkyl groups include, without limitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.

[0014] The term "cycloalkyl" refers to saturated and partially unsaturated cyclic hydrocarbon groups having the indicated number of ring carbon atoms. Preferably, cycloalkyl contains 3 to 8 carbons, and more preferably 3 to 7 carbons. Preferred cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, and cyclooctyl. The cycloalkyl group may be optionally substituted with linear or branched C1-C8 alkyl.
As noted above, in one aspect the invention provides a copolymer. Monomer units of formula I are as shown in Table 1.









[0015] The following compounds are believed to be novel: 2-methyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 3-hydroxy-2-methyl-2-nitropropyl acrylate; 3-hydroxy-2-methyl-2-nitropropyl methacrylate; 2-ethyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-(hydroxymethyl)-2-nitrobutyl acrylate; 2-(hydroxymethyl)-2-nitrobutyl methacrylate; 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl methacrylate; 2-(hydroxymethyl)-2-nitropropane-1,3-diyl diacrylate; 2-(hydroxymethyl)-2-nitropropane-1,3-diyl bis(2-methylacrylate); 3-nitrooctan-4-yl acrylate; 3-nitrooctan-4-yl methacrylate; 2-((methacryloyloxy)methyl)-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-methyl-2-nitrobutyl acrylate; 2-methyl-2-nitrobutyl methacrylate; (1-nitrocyclohexyl)methyl acrylate; (1-nitrocyclohexyl)methyl methacrylate; l-(nitromethyl)cyclohexyl acrylate; 1-(nitromethyl)cyclohexyl methacrylate; N-(2-methyl-2-nitropropyl)methacrylamide; N,N-bis(2-methyl-2-nitropropyl)acrylamide; N,N-bis(2-methyl-2-nitropropyl)methacrylamide; 2,5,6-trimethyl-2,6-dinitroheptan-3-yl acrylate; 2,5,6-trimethyl-2,6-dinitroheptan-3-yl methacrylate; N-isopropyl-N-(2-nitrobutyl)acrylamide; and N-isopropyl-N-(2-nitrobutyl)methacrylamide.

[0016] Monomer units of formula I may be readily prepared by forming the appropriate nitroalcohol or nitroamine via a standard Henry or Mannich reaction respectively, followed by capping the resultant -OH or -NH groups with an acrylate or methacrylate moieties.

[0017] Henry reactions are typically performed by mixing a nitroalkane and a base catalyst (typically a tertiary alkyl amine) in an inert solvent (typically water or lower alcohols) and adding the aldehyde to the resultant mixture at temperatures from 25-100°C. Mannich reactions are typically performed by mixing a nitroalkane and an aldehyde together in an inert solvent (typically water or lower alcohols), and slowly adding the amine to the resultant mixture at temperatures between 25 and 100°C. The resultant products may be isolated using standard techniques, such as distillation or crystallization.

[0018] There are a variety of methods that can be used to cap either the -OH or -NH moieties with a (meth)acrylate unit. Common methods include reaction of the alcohol with acryloyl chloride or acrylic anhydride.

[0019] According to the invention, the monomer unit of formula I as described above is copolymerized with a one or more other comonomers to form a copolymer. Suitable comonomers for the copolymerization are esters or amides of acrylic acid or methacrylic acid, or their mixtures. Thus, the comonomer may be, for instance, acrylic acid, methacrylic acid, esters thereof (acrylates and methacrylates), including the methyl-, butyl-, ethyl-, and 2-ethylhexyl esters of acrylic acid or methacrylic acid, acrylamide, methacrylamide, or other derivatives thereof (e.g., phosphoethyl methacrylate, acetoacetoxyethyl methacrylate), or mixtures of two or more thereof. Additional comonomers may also be included in the copolymer including, but not limited to, styrene.

[0020] In some embodiments, the amount of monomer unit of formula I in the copolymer is at least 0.5% by weight, with the balance being the other comonomers in the polymer, including the acrylic and methacrylic compounds and derivatives and styrene, if present. In some embodiments, the amount of the monomer unit of formula I in the copolymer is no more than 80 %, alternatively no more than 50%.

[0021] An aqueous emulsion of the copolymer may typically be prepared by emulsion polymerization. The emulsion polymerization can be carried out by methods well known in the polymer art, and includes multiple stage polymerization processes. Various synthesis adjuvants such as initiators, chain transfer agents, and surfactants are optionally utilized in the polymerization. In general, the reaction vessel is charged with water, and optionally surfactants and other polymerization adjuvants and optionally a polymer seed, then a part of the monomers for the polymer matrix is added to the kettle, and finally the remainder of the monomer for the polymer matrix is added to the kettle. The polymerization may be run as a shot process, or by using multiple shots, or by continuously feeding in the monomer over time. The monomer may be added neat or emulsified in water with appropriate surfactants.

[0022] The copolymer as described above is useful as binder for an aqueous based paint or coating or for other applications, such as adhesive, sealant, primer, caulk, or filler formulations.

[0023] Some embodiments of the invention will now be described in detail in the following Examples.

EXAMPLES



[0024] General. Nitrofunctional acrylate monomers may be prepared by a variety of techniques, for instance using the method described in Takahashi et al., J. Appl. Polym. Sci. 1968, 12, 1683-1695. In a typical preparation, a nitroalcohol compound and an equimolar or slight excess of acryloyl chloride or methacryloyl chloride are mixed in a suitable solvent. The mixture is stirred at elevated temperature until sufficient reaction has occurred, typically 12 to 24 hours. Following reaction, unreacted materials may be removed by distillation and the product washed with water and dried over anhydrous sodium sulfate. Purification of the product may be carried out using known techniques, such as distillation under reduced pressure. The desired structure may be confirmed using FTIR, 13C and 1H NMR, or GC/MS.

Example 1. Preparation of 2-Nitro-2-Methylpropyl Methacrylate (NMPMA)



[0025] The title compound may be prepared through substantially the same procedure as described above, using 2-nitro-2-methyl-1-propanol and 1 equivalent of acrylic chloride as the starting materials.

Example 2. Preparation of 3-hydroxy-2-methyl-2-nitropropyl acrylate



[0026] The title compound may be prepared through substantially the same procedure as described above, using 2-nitro-2-methyl-1,3-propanediol and 1 equivalent of acryloyl chloride as the starting materials.

Example 3. Preparation of Preparation of 2-methyl-2-nitropropane-1,3-diyl diacrylate



[0027] The title compound may be prepared through substantially the same procedure as described above, using 2-nitro-2-methyl-1,3-propanediol and 2 equivalents of acryloyl chloride as the starting materials.

Example 4. Preparation of 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl methacrylate



[0028] The title compound may be prepared through substantially the same procedure as described above, using tris(hydroxymethyl)nitromethane and 1 equivalent of methacryloyl chloride as the starting materials.

Example 5. Preparation of l-(nitromethyl)cyclohexyl methacrylate



[0029] The title compound may be prepared through substantially the same procedure as described above, using 1-nitromethyl-cyclohexanol and 1 equivalent of methacryloyl chloride as the starting materials.

Example 6. Preparation of N,N-bis(2-methyl-2-nitropropyl)acrylamide



[0030] A 100mL round bottom flask is charged with N,N-bis(2-methyl-2-nitropropyl)amine (0.01mol, 1 eq.), diethyl ether (50mL) and triethylamine (1.1g,1.1eq). The clear colorless solution is cooled to 5°C using an ice bath. To the stirred solution under nitrogen, acryloyl chloride (0.9g, 1eq) dissolved in 5 mL diethyl ether is added dropwise over a period of 30 minutes. After stirring for an additional 2 hours, the mixture is filtered to remove the precipitated triethylamine-hydrochloride, the clear, colorless organic solution is washed with dilute hydrochloric acid (5% aqueous, 50mL), saturated aqueous sodium bicarbonate (50mL) and water (50mL). After drying over magnesium sulfate and filtration, the solvent is removed on a rotary evaporator resulting in a light tan solid product. GC analyses indicates 95% purity. The desired structure is confirmed using FTIR, C and HNMR, and GC/MS.

Example 7. Preparation of 2,5,6-trimethyl-2,6-dinitroheptan-3-yl methacrylate



[0031] The title compound may be prepared through substantially the same procedure as described above, using 2,5,6-trimethyl-2,6-dinitroheptan-3-ol and 1 equivalent of methacryloyl chloride as the starting materials.

Example 8. Preparation of N-isopropyl-N-(2-nitrobutyl)methacrylamide



[0032] The title compound may be prepared through substantially the same procedure as described in Example 6, using N-isopropyl-N-(2-nitrobutyl)amine and 1 equivalent of methacryloyl chloride as the starting materials.

Example 9. Synthesis of Acrylic 1 (Inventive Copolymer)



[0033] A polymer having the composition 9.8 STY (styrene) / 29.9 EHA (2-ethylhexyl acrylate) / 47.2 MMA (methyl methacrylate) / 5 AAEM (acetoacetoxyethyl methacrylate) / 5 NMPMA (2-nitro-2-methylpropyl methacrylate) / 3.2 PEM (phosphoethyl methacrylate) is prepared as follows:
A monomer emulsion is prepared using 220.3 g deionized (DI) water, 17.6 g (30.4% active) anionic surfactant, 90.5 g STY, 276 g EHA, 433.7 g MMA, 45.5 g AAEM, 45.5 g NMPMA, and 29.0 g PEM. A three-liter, 4-neck round bottom flask containing an initial charge of 588.7 g DI water and a solution of 17.1 g of anionic surfactant (30.4% active) in 16.1 g DI water, followed by a rinse of 5 g DI water, is heated to 87°C under nitrogen sweep. An aliquot of monomer emulsion (29.6 g) is added to the flask along with a rinse of 10 g DI water, which is followed by the addition of a solution of 3.2 g APS (ammonium persulfate)) in 20 g DI water and a rinse of 5 g DI water. After stirring for 5 min, the remaining monomer emulsion and a solution of 1.4 g APS in 36.7 g DI water are added separately to the flask over 120 min. The contents of the reaction flask are maintained at 86°C during the addition of the monomer emulsion. When all the additions are complete the monomer emulsion container is rinsed with 44 g DI water and the APS container is rinsed with 5 g of water, which are added to the reaction flask. The reaction flask is cooled to 70°C and a t-butyl hydroperoxide/isoascorbic acid redox pair is added. The polymer is neutralized with aqueous ammonia (28%). The solid content is 45.0%.

Example 10. Synthesis of Acrylic 2 (Control (Comparative) Copolymer)



[0034] A polymer having the composition 9.8 STY / 29.9 EHA / 52.2 MMA / 5 AAEM / 3.2 PEM is prepared as follows:
A monomer emulsion is prepared using 474 g DI water, 38.5 g (30.4% active) anionic surfactant, 195 g STY, 594 g EHA, 1000 g MMA, 97.5 g AAEM, and 62.4 g PEM. A five-liter, 4-neck round bottom flask containing an initial charge of 1360 g DI water and a solution of 37.4 g of anionic surfactant (30.4% active) in 32 g DI water, followed by a rinse of 26 g DI water, is heated to 87°C under nitrogen sweep. An aliquot of monomer emulsion (63.7 g) is added to the flask along with a rinse of 42 g DI water, which is followed by the addition of a solution of 6.8 g APS in 42 g DI water and a rinse of 10 g DI water. After stirring for 5 min, the remaining monomer emulsion and a solution of 2.9 g APS in 79 g DI water are added separately to the flask over 120 min. The contents of the reaction flask are maintained at 86°C during the addition of the monomer emulsion. When all the additions are complete the monomer emulsion container is rinsed with 42 g DI water and the APS container is rinsed with 5 g of water, which are added to the reaction flask. The reaction flask is cooled to 70°C and a t-butyl hydroperoxide / isoascorbic acid redox pair is added. The polymer is neutralized with aqueous ammonia (28%). The solid content is 45.0%.

Example 11. Clear Coating Formulations and Testing



[0035] Testing Techniques. Coating gloss is determined in accordance with ASTM-D523 using a Byk-Gardner micro-tri-gloss gloss meter. Konig or pendulum hardness is measured according to ASTM D4366 using a TQC SP0500 Pendulum Hardness Tester after 1 and 7 days of coating drying, and is reported in seconds. Pencil hardness is determined in accordance with ASTM Test method D3363 - 05 after 1 and 7 days of coating drying. The pencil is held firmly against the film at a 45° angle (pointed away from the operator) and pushed away from the operator in a 6.5-mm (1/4-in.) stroke. The process is started with the hardest pencil and continued down the scale of hardness to the pencil that will not cut into or gouge the film. The hardness of this last pencil used is rated as the pencil hardness of the coatings, as from soft to hard, 6B-5B-4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H-7H-8H.

[0036] A coating formulation as shown in Table 2 is prepared.
Table 2
Raw MaterialFunctionwt %
Acrylic Polymer Binder or Polymer 76.73
Water Carrier 10.95
Rhoplex WP-11 Plasticizer 3.00
Dowanol DPnB2 Coalescing Agent 3.81
Tego Foamex 14883 Defoamer 0.06
Tego Glide 4104 Glide, anti-crater and anti-scratch additive 0.25
Dowanol DPM5 Solvent 0.25
Michelman ME-392356 Antiblocking Scratch/ Scrub/ Mar resistance agent 4.75
Byk 3467 Wetting Agent 0.01
Acrysol RM-8258 Rheology Modifier 0.19
     
Totals   100.00
1. A plasticizer from The Dow Chemical Company; 2. A coalescent agent from Dow; 3. A defoamer by Evonik Industries; 4. A glide and anti-crater additive with scratch resistance by Evonik Industries; 5. A solvent from Dow; 6. An antiblocking and Scratch/ Scrub/ Mar resistance agent by Michelman; 7. A wetting agent by BYK Chemie; and 8. A Rheology Modifier from Dow.

Testing on Treated Aluminum



[0037] Coatings are applied to a treated aluminum panel (Q panel Type Al-412 from Q-Lab Corporation chromate pretreated aluminum) using a drawdown bar with a 10 mil gap to yield dry films of approximately 2 mil thickness. The panels are air cured and the gloss, Konig hardness and pendulum hardness are measured. Results are shown in Table 3.
Table 3
BinderAcrylic 1 (inventive)Acrylic 2 (comparative)
Gloss - treated Al  
20° 93.3 75.6
60° 116.0 111.0
Konig Hardness (seconds)  
1 day 20.2 15.9
7 day 38.6 31.9
Pencil Hardness  
1 day 3B 5B
7 day 3B 3B

Chemical Testing on Maple



[0038] For chemical testing on maple boards, the coatings are sprayed at a thickness of 4 wet mil, allowed to dry, sanded with 180 grit sandpaper then sprayed with a topcoat of the same material at 4 wet mil. The chemical resistance is tested after allowing the coatings to cure at room temperature for 7 days. Testing is performed by putting a 23 mm diameter Whatman filter paper on the board and saturating it with the chemical. The chemical puddles are then covered with caps to prevent / limit evaporation during the test. After the appropriate time (1 hour or 16 hour) the chemical and filter paper are washed off and the board is dried. All samples are graded 1-10 where 10 indicates no visible sign or softening of the coating and 1 indicates complete removal / dissolution of the film.
Table 4
BinderAcrylic 1 (inventive)Acrylic 2 (comparative)
1 hour  
Ethanol 8 6
IPA 1 1
Butyl Acetate 1 1
Acetone 8 1
16 hour  
Water 7 5
Hot coffee 10 10
50% Ethanol 9 7
409 Cleaner 8 8
IPA 5 3
7% Ammonia 10 10
Red Ink 9 10
Lemon juice 10 10
Grape juice 10 10
Mustard 7 7

Summary



[0039] An acrylic polymer containing 5% of the nitro monomer NMPMA shows improvement over a control polymer in several areas: gloss, Konig hardness, Pencil hardness (including early hardness), and chemical/solvent resistance.


Claims

1. A copolymer comprising a polymerized compound of 2-methyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 3-hydroxy-2-methyl-2-nitropropyl acrylate; 3-hydroxy-2-methyl-2-nitropropyl methacrylate; 2-ethyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-(hydroxymethyl)-2-nitrobutyl acrylate; 2-(hydroxymethyl)-2-nitrobutyl methacrylate; 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl methacrylate; 2-((methacryloyloxy)methyl)-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-methyl-2-nitrobutyl acrylate; 2-methyl-2-nitrobutyl methacrylate; N-(2-methyl-2-nitropropyl)methacrylamide; N,N-bis(2-methyl-2-nitropropyl)acrylamide; N,N-bis(2-methyl-2-nitropropyl)methacrylamide; N-isopropyl-N-(2-nitrobutyl)acrylamide; or N-isopropyl-N-(2-nitrobutyl)methacrylamide.
 
2. The copolymer of claim 1, wherein the copolymer further comprises a polymerized monomer selected from acrylic acid, methacrylic acid, acrylate ester, methacrylate ester, acrylamide, methacrylamide, or mixtures of two or more thereof.
 
3. The copolymer of claim 2, wherein the acrylate and methacrylate are selected from methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phosphoethyl methacrylate, acetoacetoxyethyl methacrylate, or a mixture of two or more thereof.
 
4. The copolymer of claims 2 or 3, wherein the copolymer further comprises polymerized styrene.
 
5. The copolymer of any one of claims 1-4, wherein the polymerized compound of claim 1 comprise no more than 80% of the copolymer.
 
6. The polymer of any one of claims 1-5, wherein the polymerized compound of claim 1 comprise no more than 50% of the copolymer.
 
7. A compound that is: 2-methyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 3-hydroxy-2-methyl-2-nitropropyl acrylate; 3-hydroxy-2-methyl-2-nitropropyl methacrylate; 2-ethyl-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-(hydroxymethyl)-2-nitrobutyl acrylate; 2-(hydroxymethyl)-2-nitrobutyl methacrylate; 3-hydroxy-2-(hydroxymethyl)-2-nitropropyl methacrylate; 2-((methacryloyloxy)methyl)-2-nitropropane-1,3-diyl bis(2-methylacrylate); 2-methyl-2-nitrobutyl acrylate; 2-methyl-2-nitrobutyl methacrylate; N-(2-methyl-2-nitropropyl)methacrylamide; N,N-bis(2-methyl-2-nitropropyl)acrylamide; N,N-bis(2-methyl-2-nitropropyl)methacrylamide; N-isopropyl-N-(2-nitrobutyl)acrylamide; or N-isopropyl-N-(2-nitrobutyl)methacrylamide.
 


Ansprüche

1. Copolymer, umfassend eine polymerisierte Verbindung von 2-Methyl-2-nitropropan-1,3-diylbis(2-methylacrylat); 3-Hydroxy-2-methyl-2-nitropropylacrylat; 3-Hydroxy-2-methyl-2-nitropropylmethacrylat; 2-Ethyl-2-nitropropan-1,3-diylbis(2-methylacrylat); 2-(Hydroxymethyl)-2-nitrobutylacrylat; 2-(Hydroxymethyl)-2-nitrobutylmethacrylat; 3 -Hydroxy-2-(hydroxymethyl)-2-nitropropylmethacrylat; 2-((Methacryloyloxy)methyl)-2-nitropropan-1,3-diylbis(2-methylacrylat); 2-Methyl-2-nitrobutylacrylat; 2-Methyl-2-nitrobutylmethacrylat; N-(2-Methyl-2-nitropropyl)methacrylamid; N,N-Bis(2-methyl-2-nitropropyl)acrylamid; N,N-Bis(2-methyl-2-nitropropyl)methacrylamid; N-Isopropyl-N-(2-nitrobutyl)acrylamid; oder N-Isopropyl-N-(2-nitrobutyl)methacrylamid.
 
2. Copolymer nach Anspruch 1, wobei das Copolymer ferner ein polymerisiertes Monomer umfasst, ausgewählt aus Acrylsäure, Methacrylsäure, Acrylatester, Methacrylatester, Acrylamid, Methacrylamid oder Gemischen aus zwei oder mehr davon.
 
3. Copolymer nach Anspruch 2, wobei das Acrylat und das Methacrylat ausgewählt sind aus Methylacrylat, Ethylacrylat, Butylacrylat, 2-Ethylhexylacrylat, Methylmethacrylat, Ethylmethacrylat, Butylmethacrylat, 2-Ethylhexylmethacrylat, Phosphoethylmethacrylat, Acetoacetoxyethylmethacrylat oder einem Gemisch aus zwei oder mehr davon.
 
4. Copolymer nach Anspruch 2 oder 3, wobei das Copolymer ferner polymerisiertes Styrol umfasst.
 
5. Copolymer nach einem der Ansprüche 1-4, wobei die polymerisierte Verbindung nach Anspruch 1 nicht mehr als 80 % des Copolymers umfasst.
 
6. Polymer nach einem der Ansprüche 1-5, wobei die polymerisierte Verbindung nach Anspruch 1 nicht mehr als 50 % des Copolymers umfasst.
 
7. Verbindung, die Folgendes ist: 2-Methyl-2-nitropropan-1,3-diylbis(2-methylacrylat); 3-Hydroxy-2-methyl-2-nitropropylacrylat; 3 -Hydroxy-2-methyl-2-nitropropylmethacrylat; 2-Ethyl-2-nitropropan-1,3-diylbis(2-methylacrylat), 2-(Hydroxymethyl)-2-nitrobutylacrylat; 2-(Hydroxymethyl)-2-nitrobutylmethacrylat; 3 -Hydroxy-2-(hydroxymethyl)-2-nitropropylmethacrylat; 2-((Methacryloyloxy)methyl)-2-nitropropan-1,3-diylbis(2-methylacrylat); 2-Methyl-2-nitrobutylacrylat; 2-Methyl-2-nitrobutylmethacrylat; N-(2-Methyl-2-nitropropyl)methacrylamid; N,N-Bis(2-methyl-2-nitropropyl)acrylamid; N,N-Bis(2-methyl-2-nitropropyl)methacrylamid; N-Isopropyl-N-(2-nitrobutyl)acrylamid; oder N-Isopropyl-N-(2-nitrobutyl)methacry lamid.
 


Revendications

1. Copolymère comprenant un composé polymérisé de bis(2-méthylacrylate) de 2-méthyl-2-nitropropane-1,3-diyle ; acrylate de 3-hydroxy-2-méthyl-2-nitropropyle ; méthacrylate de 3-hydroxy-2-méthyl-2-nitropropyle ; bis(2-méthylacrylate) de 2-éthyl-2-nitropropane-1,3-diyle ; acrylate de 2-(hydroxyméthyl)-2-nitrobutyle ; méthacrylate de 2-(hydroxyméthyl)-2-nitrobutyle ; méthacrylate de 3-hydroxy-2-(hydroxyméthyl)-2-nitropropyle ; bis(2-méthylacrylate) de 2-((méthacryloyloxy)méthyl)-2-nitropropane-1,3-diyle ; acrylate de 2-méthyl-2-nitrobutyle ; méthacrylate de 2-méthyl-2-nitrobutyle ; N-(2-méthyl-2-nitropropyl)méthacrylamide ; N,N-bis(2-méthyl-2-nitropropyl)acrylamide ; N,N-bis(2-méthyl-2-nitropropyl)méthacrylamide ; N-isopropyl-N-(2-nitrobutyl)acrylamide ; ou de N-isopropyl-N-(2-nitrobutyl)méthacrylamide.
 
2. Copolymère de la revendication 1, le copolymère comprenant en outre un monomère polymérisé choisi parmi l'acide acrylique, l'acide méthacrylique, un ester d'acrylate, un ester de méthacrylate, l'acrylamide, le méthacrylamide, ou des mélanges de deux d'entre eux ou plus.
 
3. Copolymère de la revendication 2, dans lequel l'acrylate et le méthacrylate sont choisis parmi l'acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de butyle, l'acrylate de 2-éthylhexyle, le méthacrylate de méthyle, le méthacrylate d'éthyle, le méthacrylate de butyle, le méthacrylate de 2-éthylhexyle, le méthacrylate de phosphoéthyle, le méthacrylate d'acétoacétoxyéthyle, ou un mélange de deux d'entre eux ou plus.
 
4. Copolymère des revendications 2 ou 3, le copolymère comprenant en outre du styrène polymérisé.
 
5. Copolymère de l'une quelconque des revendications 1 à 4, dans lequel le composé polymérisé de la revendication 1 ne constitue pas plus de 80 % du copolymère.
 
6. Polymère de l'une quelconque des revendications 1 à 5, dans lequel le composé polymérisé de la revendication 1 ne constitue pas plus de 50 % du copolymère.
 
7. Composé qui est : le bis(2-méthylacrylate) de 2-méthyl-2-nitropropane-1,3-diyle ; l'acrylate de 3-hydroxy-2-méthyl-2-nitropropyle ; le méthacrylate de 3-hydroxy-2-méthyl-2-nitropropyle ; le bis(2-méthylacrylate) de 2-éthyl-2-nitropropane-1,3-diyle ; l'acrylate de 2-(hydroxyméthyl)-2-nitrobutyle ; le méthacrylate de 2-(hydroxyméthyl)-2-nitrobutyle ; le méthacrylate de 3-hydroxy-2-(hydroxyméthyl)-2-nitropropyle ; le bis(2-méthylacrylate) de 2-((méthacryloyloxy)méthyl)-2-nitropropane-1,3-diyle ; l'acrylate de 2-méthyl-2-nitrobutyle ; le méthacrylate de 2-méthyl-2-nitrobutyle ; le N-(2-méthyl-2-nitropropyl)méthacrylamide ; le N,N-bis(2-méthyl-2-nitropropyl)acrylamide ; le N,N-bis(2-méthyl-2-nitropropyl)méthacrylamide ; le N-isopropyl-N-(2-nitrobutyl)acrylamide ; ou le N-isopropyl-N-(2-nitrobutyl)méthacrylamide.
 






Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description