WO2023212495A1

WO2023212495A1 - Novel bio-based compound, method of forming the compound, and adhesive compositions containing the novel compound

Info

Publication number: WO2023212495A1
Application number: PCT/US2023/065944
Authority: WO
Inventors: Mavyn Holman; Nandita BHAGWAT; Yan Meng; Ke Li; Jason Patrick SAFKO; Christopher HORNAT; Matthew Hernandez; Md Nazim UDDIN; Ranga Ranganathan; Christie SUTANTO
Original assignee: Zymergen Inc.
Priority date: 2022-04-29
Filing date: 2023-04-19
Publication date: 2023-11-02

Abstract

A compound can have a structure of formula (1) or formula(2): [insert figure] with R1, R2 being independently H, or alkyl, or alkylaryl, or X1, or X2; X1, X2 independently being [insert figure], [insert figure], [insert figure], or [insert figure]; and Y1 being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10. The compound can be included in an adhesive composition to adjust a desired property profile of the adhesive.

Description

NOVEL BIO-BASED COMPOUND, METHOD OF FORMING THE COMPOUND, AND

ADHESIVE COMPOSITIONS CONTAINING THE NOVEL COMPOUND

TECHNICAL FIELD

The present disclosure relates to novel bio-based compounds and adhesive compositions containing the novel compounds.

BACKGROUND ART

Adhesives are highly desirable in many applications, particularly for optical displays and electronics. As electronic devices become smaller and smaller, new challenges arise on the adhesives, such as higher performance in a smaller and tighter space.

There exists a need to develop bio-based adhesive systems having improved modulus and impact resistance without compromising the glass transition temperature.

SUMMARY

Various aspects and embodiments contemplated herein may include, but are not limited to one or more of the following.

In one embodiment, a compound can have a structure of formula (1) or formula(2):

with Rl, R2 being independently H, or alkyl, or alkylaryl, or XI, or X2;

Y 1 being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10.

In another embodiment, an adhesive composition can comprise at least one compound having a structure of formula (1) or formula (2):

with Rl, R2 being independently H, or alkyl, or alkylaryl, or XI, or X2;

Y 1 being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10.

In a further embodiment, a method of forming a compound can comprise: forming an amino acid dimer of an amino acid; alkoxylating the amino acid dimer with an alkyl oxide to form an alkoxylated amino acid dimer; and introducing at least one functional group on the alkoxylated amino acid dimer, the functional group being selected from hydroxyl, epoxy, acrylate, alkylacrylate, or isocyanate, wherein the compound has a structure of formula (1) or formula (2):

with Rl, R2 being independently H, or alkyl, or alkylaryl, or XI, or X2;

Y 1 being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10. BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure may be better understood, and its numerous features and advantages made apparent to those skilled in the art by referencing the accompanying drawings.

FIG. 1 includes a scheme illustrating a method of making the novel bio-based compound according to one embodiment.

The use of the same reference symbols in different drawings indicates similar or identical items.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following description in combination with the figures is provided to assist in understanding the teachings disclosed herein. The following discussion will focus on specific implementations and embodiments of the teachings. This focus is provided to assist in describing the teachings and should not be interpreted as a limitation on the scope or applicability of the teachings.

As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such process, method, article, or apparatus.

As used herein, and unless expressly stated to the contrary, “or” refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are illustrative only and not intended to be limiting. To the extent not described herein, many details regarding specific materials and processing acts are conventional and may be found in reference books and other sources within the structural arts and corresponding manufacturing arts. Unless indicated otherwise, all measurements are at about 23 °C +/- 5 °C per ASTM, unless indicated otherwise.

The present disclosure is directed to a novel compound falling under formula (1) or (2) described above. As used herein, if not indicated otherwise, the compound falling under formula (1) or (2) is interchangeable also called “functionalized cyclic amino acid dimer” of the present disclosure.

As illustrated in the scheme of FIG. 1 , a method of making the compound of the present disclosure can include: forming a cyclic amino acid dimer of an amino acid (11); alkoxylating the amino acid dimer with an alkoxyl oxide to form an alkoxylated amino acid dimer (12); and introducing at least one functional group on the alkoxylated amino acid dimer (13).

In one aspect of the method, the amino acid for forming the amino acid dimer (step 11) can be selected from tyrosine, hydroxyproline, phenylalanine, or glycine.

In a further aspect of the method, alkoxylating the amino acid dimer (step 12) to an alkoxylated amino acid dimer can be conducted by reacting the hydroxyl groups and amine groups of the amino acid dimer with an alkyloxide selected from the group of ethylene oxide, propylene oxide, or butylene oxide. In a particular aspect, the alkyloxide can be propylene oxide.

In step (13) of the method, the alkoxylated amino acid dimer can be subjected to further introducing at least one functional group. In aspects, the at least one functional group can be a hydroxyl group, an epoxy group, an acrylate group, an alkylacrylate group, or an isocyanate group.

In a certain particular aspect, the alkoxylated amino acid dimer can be functionalized by introducing one or more epoxy groups, also called herein epoxidation. The epoxidation reaction can be stoichiometric, such that one mole of epichlorohydrin or epibromohydrin is used per mole of hydroxy groups in the moiety. Alternatively, the molar ratio of epoxidizing agent to hydroxy groups of the alkoxylated amino acid dimer can vary within a range from 20: 1 to 0.9: 1, such as from 15:1 to 1: 1, 10: 1 to 1 : 1, or 5:1 to 1: 1.

In one embodiment, the compound of the present disclosure can have a structure of formula (3):

with R1 and R2 being independently H, or alkyl, or alkylaryl; and Zl, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m being 1-10. In a particular aspect, the compound may have a structure of formula (4):

In another embodiment, the compounds of the present disclosure may have the structure of formula (5):

, or hydrogen, or alkyl, or alkylaryl;

Zl, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m independently being 1-10. In a certain aspect, the compound can have the structure of formula (6), with n, m, x, y independently being 1-10.

In yet a further embodiment, the compound of the present disclosure can have the structure of formula (7):

independently being 1-10.

In one further embodiment, the compound of the present disclosure can have a bio-based carbon content of at least 10%, such as at least 15%, at least 20%, at least 25%, at least 30%, or at least 35%, as determined by ASTM D6866. Bio-based carbon content as defined herein is the percentage of carbons from renewable or biogenic sources, such as plants or animals over the total number of carbons in the compound.

The present disclosure is further directed to an adhesive composition comprising the compound falling under formula (1) or (2) as described in embodiments above, or a combination thereof.

In one aspect, the amount of the compound of formula (1) or (2) in the adhesive composition can be at least 5 wt% based on the total weight of the adhesive composition, such as at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, or at least 50 wt%, or at least 55 wt%. In another aspect, the amount of the compound in the adhesive composition may be not greater than 70 wt% based on the total weight of the adhesive composition, such as not greater than 60 wt%, or not greater than 55 wt%, or not greater than 50 wt%. The adhesive composition can include next to the compound of formula (1) or (2) at least one second compound, wherein the at least one second compound is adapted to react with the functional groups of the compound of formula (1) or (2).

In a certain aspect, the second compound can be an amine compound. In a particular aspect, the amine compound may includes m-xylenediamine or 1,13 diamino-4,7,10 trioxatridecane.

In further embodiments, the adhesive composition can include one or more further additives, for example, a solvent, a filler, a dye, a viscosity modifying agent, a dispersing agent, or a curing initiator.

The use of the compound of the present disclosure in adhesive compositions can have an advantage to obtain adhesives having improved lap shear strength, elongation, and impact resistance without compromising the glass transition temperature.

The use of the compound of the present disclosure may not be limited to adhesives, but the compound can be also employed in a composite, a coating, an electronic device, an energy storage device, or an energy generation device.

Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, skilled artisans will appreciate that those aspects and embodiments are only illustrative and do not limit the scope of the present invention. Embodiments may be in accordance with any one or more of the items as listed below.

Embodiments:

Embodiment 1. A compound having a structure of formula (1) or formula(2):

with Rl, R2 being independently H, or alkyl, or alkylaryl, or XI, or X2;

Y 1 being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10. Embodiment 2. The compound of embodiment 1, having the structure of formula (3):

with R1 and R2 being independently H, or alkyl, or alkylaryl; and

Zl, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m being 1-10.

Embodiment 3. The compound of embodiment 2, comprising a structure of formula (4):

with n, m independently being 1-10.

Embodiment 4. The compound of embodiment 1, having the structure of formula (5):

with R3 or R4 being

, or hydrogen, or alkyl, or alkylaryl;

Zl, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m independently being 1-10.

Embodiment 5. The compound of embodiment 4, comprising a structure of formula (6):

with n, m, x, y independently being 1-10.

Embodiment 6. The compound of embodiment 1, comprising a structure of formula (7):

with n, m independently being 1-10.

Embodiment 7. An adhesive composition comprising at least one compound having a structure of formula (1) or formula (2):

with Rl, R2 being independently H, or alkyl, or alkylaryl, or XI, or X2;

Y 1 being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10. Embodiment 8. The adhesive composition of embodiment 7, the adhesive composition comprising a compound having a structure of formula (3):

with R1 and R2 being independently H, or alkyl, or alkylaryl; and Zl, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m being 1-10.

Embodiment 9. The adhesive composition of embodiment 8, wherein the adhesive composition comprises a compound having a structure of formula (4):

with n, m independently being 1-10.

Embodiment 10. The adhesive composition of embodiment 7, comprising a compound having a structure of formula (5):

or hydrogen, or alkyl, or alkylaryl;

Embodiment 11. The adhesive composition of embodiment 10, wherein the adhesive composition comprises a compound having a structure of formula (6):

with n, m, x, y independently being 1-10.

Embodiment 12. The adhesive composition of embodiment 7, comprising a structure of formula (7):

with n, m independently being 1-10. Embodiment 13. The adhesive composition of any one of embodiments 7-12, wherein the adhesive composition further comprises an amine compound.

Embodiment 14. The adhesive composition of embodiment 13, wherein the amine compound includes m-xylenediamine or 1,13 diamino-4,7,10 trioxatridecane.

Embodiment 15. A method of forming a compound, comprising: forming an amino acid dimer of an amino acid; alkoxylating the amino acid dimer with an alkyl oxide to form an alkoxylated amino acid dimer; and introducing at least one functional group on the alkoxylated amino acid dimer, the functional group being selected from hydroxyl, epoxy, acrylate, alkylacrylate, or isocyanate.

Embodiment 16. The method of embodiment 15, wherein the amino acid is selected from tyrosine, hydroxyproline, or glycine.

Embodiment 17. The method of embodiments 15 or 16, wherein the alkyloxide is selected from ethylene oxide, propylene oxide or butylene oxide.

Embodiment 18. The method of embodiment 17, wherein the alkyl oxide comprises propylene oxide.

Embodiment 19. The method of any one of embodiments 15-18, wherein the functional group is an epoxy group.

Embodiment 20. The method of embodiment 19, wherein introducing the at least one epoxy group comprises reacting the alkoxylated amino acid dimer with epichlorohydrine.

Embodiment 21. The method of any one of embodiments 15-20, wherein the compound has a structure of formula(l) or formula (2):

with Rl, R2 being independently H, or alkyl, or alkylaryl, or XI, or X2;

Y 1 being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10.

Embodiment 22. The method of embodiment 21, wherein the compound has a structure of formula (3):

with R1 and R2 being independently H, or alkyl, or alkylaryl; and

Zl, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m being 1-10. Embodiment 23. The compound of embodiment 22, wherein the compound has a structure of formula (4):

with n, m independently being 1-10.

Embodiment 24. The method of embodiment 21, wherein the compound has a structure of formula (5):

with R3 or R4 being

, or hydrogen, or alkyl, or alkylaryl;

Embodiment 25. The method of embodiment 24, wherein the compound has a structure of formula (6):

with n, m, x, y independently being 1-10.

Embodiment 26. The method of embodiment 21, wherein the compound has a structure of formula (7):

with n, m independently being 1-10.

The following examples are provided to better disclose and teach processes and compositions of the present invention. They are for illustrative purposes only, and it must be acknowledged that minor variations and changes can be made without materially affecting the spirit and scope of the invention as recited in the claims that follow.

EXAMPLES

Example 1

Propoxylation of amino-acid dimers. The amino-acid dimer of tyrosine was made by mixing 200 g of tyrosine and 800 ml ethylene glycol in a 3L two-neck round bottom flask equipped with magnetic stirrer and overhead condenser. The flask was heated with an oil bath to 190 °C and the reaction mixture was stirred for 7h at this temperature. The conversion of starting material to the dimer was followed up by HPLC. After cooling the reaction mixture down to room temperature, the precipitated solid was filtered and washed with ethanol (2x 200ml). The solid was dried in a vacuum oven. The yield of the tyrosine amino acid dimer (TAD) was 64%.

The TAD was propoxylated according to the following procedure: In a reaction vessel, 16.32 g of TAD, 13.821 g of potassium carbonate, and 100 ml dimethyl sulfoxide were added and stirred under nitrogen for about 15 minutes. Thereafter, 11.61 g of propylene oxide was added to the reactor and the reaction mixture heated to 100°C and held at this temperature for about 5 hours.

Thereafter, the reaction product was discharged from the reactor into a separatory funnel where it was neutralized with 12.6 Molar hydrochloric acid. After reaching a pH between 6-7, the product was washed by rinsing three times with dichloromethane (DCM). The DCM containing layer was separated from the aqueous layer, washed with deioinized water three times, followed by washing three times with brine, drying with magnesium sulfate and filtering. Thereafter, the DCM was removed by rotary evaporation and the remaining product dried overnight under vacuum at a temperature between 80-90°C.

A summary of the conducted reaction is shown in reaction equation R11-A below.

In a similar procedure as described above for tyrosine, the amino acid dimer of glycine was made and propoxylated. The glycine amino acid dimer (GAD) was propoxylated using for the propoxylation 5.71 g of GAD, 0.281 g of KOH, and 100 ml DMSO, see reaction equation R12-A below.

R12-A:

Furthermore, in a similar procedure the amino acid dimer of hydroxyproline was made and propoxylated. The hydroxyproline amino acid dimer (HP AD) was propoxylated using 7.92 g HP AD, 0.196 g KOH, 100 ml DMSO, and 12.4 g propylene oxide. See also reaction equation R13-A below.

Furthermore, the dimer of amino acid of phenylalanine was synthesized and propoxylated. The phenylanaline amino acid dimer (PAD) was propoxylated using 10.30 g PAD, 0.191 g KOH, 100 ml DMSO, and 4.27 g propylene oxide. See also reaction equation R14-A below.

Example 2

Diglycidilation of propoxylated amino acid dimers.

The propoxylated amino acid dimers of Example 1 were further subjected to a diglycidilation reaction according to the following general procedure: 0.1 eq of tetrabutylammonium hydrogen sulfate (Bu4NHSO4) and 10 eq of solid sodium hydroxide (NaOH) were added to a round bottom flask and stirred under nitrogen. Thereafter, a solution of

1 eq propoxylated compound in 20 eq of epichlorohydrin was added, followed by adding 0.33 eq. of water. The round bottom flask was heated to about 40°C and the temperature maintained for about 12 hours. After cooling to room temperature, the reaction mixture was diluted with ethylactetate, and filtered to remove solid by-products. The clear organic phase was condensed and purified via silica gel chromatography to obtain the pure reaction products, see also reaction equations Rl l-B, R12-B, R13-B, and R14-B below. Rl l-B:

(6)

R12-B:

(7) R14-B:

(8) Example 3

Performance Testing:

For each of the bio-based epoxy compounds made in Example 2, the epoxy equivalent weight (EEW) was calculated according to ASTM DI 652-11.

Furthermore, the compounds were tested via modulated differential scanning calorimetry (MDSC) and the first and second heat peak recorded.

Table 1 shows a summary of the test results, together with the results of commercial product E828, a difunctional bisphenol A- epichlorohydrin, which is a known amine-reactive adhesive component, and used as comparative sample.

Table 1

Adhesive compositions were prepared with each of the epoxy compound listed in Table 1, by combining 1: 1 volume equivalents of epoxy compound with m-xylenediamine (mXDA).

Curing of the adhesive compositions was conducted by heating for 1 hour at 70°C, followed by heating for 2 hours at 175°C.

Table 2 summarizes measured properties of the adhesive compositions, such as cure peak enthalpy, cure peak temperature, glass transition temperature (tan 8 of storage modulus curve) and storage modulus at 25 °C (approximate room temperature modulus) and 200 °C (rubbery state modulus, which gives a measure of crosslink density).

Table 2

It can be seen that compounds (6), (4), (7) and (8) are suitable for use in adhesive compositions. Especially sample SI, containing an epoxy compound with a structure of formula (6), had a higher glass transition temperature, storage modulus (at both 25 °C and 200 °C) than comparative sample Cl.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention. Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

After reading the specification, skilled artisans will appreciate that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, references to values stated in ranges include each and every value within that range.

Claims

WHAT IS CLAIMED IS:

1. A compound having a structure of formula (1) or formula(2):

with Ri, R2 being independently H, or alkyl, or alkylaryl, or Xi, or X2;

Yi being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10.

2. The compound of claim 1, having the structure of formula (3):

with Ri and R2 being independently H, or alkyl, or alkylaryl; and

Zi, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m being 1-10.

3. The compound of claim 2, comprising a structure of formula (4):

with n, m independently being 1-10.

4. The compound of claim 1, having the structure of formula (5): with R3

r hydrogen, or alkyl, or alkylaryl;

Zi, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; and n, m independently being 1-10.

5. The compound of claim 4, comprising a structure of formula (6):

with n, m, x, y independently being 1-10.

The compound of claim 1, comprising a structure of formula (7):

with n, m independently being 1-10. An adhesive composition comprising at least one compound having a structure of formula (1) or formula (2):

with Ri, R2 being independently H, or alkyl, or alkylaryl, or Xi, or X2;

Yi being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10. The adhesive composition of claim 7, the adhesive composition comprising a compound having a structure of formula (3):

with Ri and R2 being independently H, or alkyl, or alkylaryl; and

9. The adhesive composition of claim 8, wherein the adhesive composition comprises a compound having a structure of formula (4):

with n, m independently being 1-10.

10. The adhesive composition of claim 7, comprising a compound having a structure of formula (5):

r hydrogen, or alkyl, or alkylaryl;

Zi, Z2 being independently hydroxyl, epoxy, acrylate, methacrylate, or isocyanate; n, m independently being 1-10.

with n, m, x, y independently being 1-10. The adhesive composition of claim 7, comprising a structure of formula (7):

with n, m independently being 1-10. The adhesive composition of claim 7, wherein the adhesive composition further comprises an amine compound. The adhesive composition of claim 12, wherein the amine compound includes m- xylenediamine or 1,13 diamino-4,7,10 trioxatridecane. A method of forming a compound, comprising: forming an amino acid dimer of an amino acid; alkoxylating the amino acid dimer with an alkyl oxide to form an alkoxylated amino acid dimer; and introducing at least one functional group on the alkoxylated amino acid dimer, the functional group being selected from hydroxyl, epoxy, acrylate, alkylacrylate, or isocyanate, wherein the compound has a structure of formula(l) or formula (2):

with Ri, R2 being independently H, or alkyl, or alkylaryl, or Xi, or X2;

Xi, X2 independently being

Yi being C1-C5 alkyl or isoalkyl; Y3 being H or C1-C3 alkyl; and n being 1-10.