WO2020206345A1

WO2020206345A1 - Enhancement of polymer mechanical properties using quinacridone additives

Info

Publication number: WO2020206345A1
Application number: PCT/US2020/026711
Authority: WO
Inventors: Lei Fang; Chenxu Wang; Hung-Jue Sue; Spencer HAWKINS; Xiaozhou JI
Original assignee: Texas A&M University System; Texas A&M University
Current assignee: Texas A&M University System; Texas A&M University
Priority date: 2019-04-04
Filing date: 2020-04-03
Publication date: 2020-10-08
Anticipated expiration: 2021-10-04

Abstract

In an embodiment, the present disclosure relates to a composition including a polymer matrix and an additive. In some embodiments, the additive is a quinacridone additive. In another embodiment, the present disclosure relates a method of making a composition. In some embodiments, the method includes adding an additive to a polymer matrix. In some embodiments, the additive is a quinacridone additive.

Description

ENHANCEMENT OF POLYMER MECHANICAL PROPERTIES USING

QUINACRIDONE ADDITIVES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims priority from, and incorporates by reference the entire disclosure of, U.S. Provisional Application No. 62/829,612 filed on April 4, 2019.

TECHNICAL FIELD

[0002] The present disclosure relates generally to enhancement of polymer mechanical properties and more particularly, but not by way of limitation, to enhancement of polymer mechanical properties using quinacridone additives.

BACKGROUND

[0003] The enhancement of mechanical properties of a polymeric material without compromising other properties (e.g., elastic modulus) in the polymeric material represents a major challenge for materials science in both academia and in industry. As such, the present disclosure describes a cost-effective strategy to achieve an enhancement of mechanical properties with a polymeric material, without compromising other properties, for example the elastic modulus of the polymeric material, on the basis of a new class of molecular additives. The present disclosure integrates chemistry, materials science, and modeling expertise to develop and optimize a new class of composite materials for a wide range of applications, such as, but not limited to, industry and defense.

SUMMARY OF THE INVENTION

[0004] In an embodiment, the present disclosure relates to a composition including a polymer matrix and an additive, where the additive is a quinacridone additive.

[0005] In another embodiment, the present disclosure relates a method of making a composition that includes adding an additive to a polymer matrix, where the additive is a quinacridone additive. [0006] In a particular embodiment, the present disclosure relates a composition including a polymer matrix and an additive, where the additive is:

or combinations thereof, and where the additive is present in an amount at or below about 1 wt%.

[0007] In a certain embodiment, the present disclosure relates a method of making a composition that includes adding an additive to a polymer matrix, where the additive is:

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] A more complete understanding of the subject matter of the present disclosure may be obtained by reference to the following Detailed Description when taken in conjunction with the accompanying Drawings wherein: [0009] FIG. 1A, FIG. IB, and FIG. 1C illustrate properties associated with epoxy compared with epoxy containing inorganic additives;

[0010] FIG. 2A, FIG. 2B, and FIG. 2C illustrate properties associated with epoxy compared with epoxy containing PCL copolymer organic additives;

[0011] FIG. 3 A and FIG. 3B illustrate properties associated with epoxy compared with epoxy containing crystal PCL copolymer organic additives; [0012] FIG. 4A, FIG. 4B, and FIG. 4C illustrate properties associated with epoxy compared with epoxy containing worm-like polymer copolymer (PEP-PEO copolymer) organic additives;

[0013] FIG. 5A, FIG. 5B, and FIG. 5C illustrate properties associated with epoxy compared with epoxy containing reactive polymer (PDMS-PGMA copolymer) additives;

[0014] FIG. 6A and FIG. 6B illustrate properties associated with epoxy compared with epoxy containing C8 IQA and C8-CH₃ IQA additives;

[0015] FIG. 7A and FIG. 7B illustrate measured Young’s modulus, strain at break, and tensile strength for epoxy, and epoxy with C8 IQA (FIG. 7A) and C8-CH₃ IQA (FIG. 7B) at various IQA content (wt%);

[0016] FIG. 8 A illustrates differential scanning calorimetry (DSC) results of epoxy and epoxy with C8 IQA additives; and

[0017] FIG. 8B illustrates dynamic mechanical analysis (DMA) results of epoxy and epoxy with C8 IQA additives.

DETAILED DESCRIPTION

[0018] It is to be understood that the following disclosure provides many different embodiments, or examples, for implementing different features of various embodiments. Specific examples of components and arrangements are described below to simplify the disclosure. These are, of course, merely examples and are not intended to be limiting. The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described.

[0019] The present disclosure relates generally to a class of compounds (organic quinacridone derivatives) that have never been used as an additive to enhance mechanical properties of polymers. In some embodiments, a series of organic quinacridone derivatives are incorporated as additives into a variety of polymer matrix systems. In various embodiments, the mechanical properties of the polymers are enhanced significantly with extremely low additive loading, typically less than ~1 wt%. The use of quinacridone additives leads to significant increase in elongation of polymer without compromising elastic modulus, which is unprecedented.

[0020] Various components can be used as additives in a polymer matrix, for example, carbon nanotubes, block copolymers, and graphene oxide. However, the additives of the present disclosure have very low loading (less than ~1 wt%) of inexpensive organic additives, compared to the competing additives presently available that typically require high loading. High additive loading significantly alters the optical and electronic properties of polymer products, for example, making them black and opaque, and less insulating. The additives of the present disclosure significantly increase the ductility of a polymer matrix without compromising other properties of the polymer matrix, such as, the elastic modulus. Currently, most available additives increase one property of the polymer matrix, however sacrifice other properties.

[0021] FIG. 1A, FIG. IB, and FIG. 1C illustrate properties associated with epoxy compared with epoxy containing inorganic additives. “P-MWCNT” refers to pristine-multiwall carbon nanotubes and “O-MWCNT” refers to oxidized multiwall carbon nanotubes. Various changes occur in the elongation, strength, modulus, and glass transition temperature (Tg) upon adding various inorganic additives. Carbon nanotubes/multiwall carbon nanotubes (CNT/MWCNT) increase the modulus; however, both strength and elongation properties of the epoxy decrease. CNT-ZnO additives increase the elongation, strength, and modulus. The addition of S1O2 decreases elongation, however increases modulus and glass transition temperature. The addition of S1O2-GO (graphene oxide) increases elongation, strength and modulus. Chemical modification is required for inorganic additives before they are added to the epoxy. Additionally, the inorganic additives require high loading.

[0022] FIG. 2A, FIG. 2B, and FIG. 2C illustrate properties associated with epoxy versus epoxy containing PCL (poly-s-caprolactone) copolymer organic additives. While elongation increases with PCL polymer additive in epoxy, strength, modulus, and glass transition temperature are all negatively affected. Furthermore, miscible polymer additives plasticize epoxy composites and, in addition, PCL polymer requires high additive loading.

[0023] FIG. 3A and FIG. 3B illustrate properties associated with epoxy versus epoxy containing crystal PCL copolymer organic additives. As indicated in FIG. 3B, epoxy with crystal PCL copolymer additive has a lower glass transition temperature (T_g) due to plasticization, and as a result, a lower modulus is seen after T_g due to the melting of the polymer. As with the previously mentioned additives, crystal PCL copolymer additive also exhibits high loading. [0024] FIG. 4A, FIG. 4B, and FIG. 4C illustrate properties associated with epoxy versus epoxy with a worm-like polymer copolymer (poly(ethylene propylene)-poly(ethylene oxide) (PEP-PEO) copolymer) organic additive. As can be seen in FIG. 4C, 5 wt% PEP-PEO copolymer in epoxy leads to higher elongation and strength properties, however the modulus declines. As illustrated by FIG. 4A, FIG. 4B, and FIG. 4C, copolymers with worm-like morphology improve mechanical properties, however these additives also require high loading.

[0025] FIG. 5A, FIG. 5B, and FIG. 5C illustrate properties associated with epoxy versus epoxy containing reactive polymer (poly(dimethyl siloxane)-poly(glycidyl methacrylate) (PDMS-PGMA) copolymer) additives. As demonstrated in Table 1 below, a 10 wt% PDMS- PGMA copolymer additive showed an increase in elongation, strength, and glass transition temperature; however, this type of additive requires chemical reactions between the additives and the epoxy. Specific functional groups are required for the additives to achieve specific properties, and, similar to the additives previously described above, with respect to FIG. 1- FIG. 4, require high loading.

Table 1

Tensile Strength Elongation at Break Young’s Modulus

ER/PDMS-PGMA

(MPa) (%) (GPa)

100/0 48.85 + 1.8 3.10 + 0.8 2.12 + 0.3

95/5 57.02 + 2.3 3.92 ± 0.6 2.18 + 0.3

90/10 61.76 + 2.5 3.74 ± 0.4 2.20 + 0.2

85/15 49.37 + 3.5 3.55 + 0.5 1.92 + 0.3

80/20 48.50 + 3.1 2.68 + 0.3 1.78 + 0.3

[0026] Table 2, shown below, provides summary information with respect to the epoxy additives O-MWCNT with ZnO, SiCk-GO, and PEP-PEO block polymer. Table 2

Additive Particle Loading (wt%) E (GPa) d (MPa) 8 (%) O-MWCNT 0 2.71 51 2.7 (with ZnO) 1.7 4.10 62 3.0

0 1.36 51.0 6.14

S1O2-GO

10 1.79 78.5 7.36

PEP-PEO Block 0 2.56 58.7 3.6 Polymer 5 2.44 63.7 8.0

[0027] In view of the foregoing, a cost-effective strategy to achieve an enhancement of mechanical properties with a polymeric material, without compromising other properties, for example the elastic modulus of the polymeric material, is needed. As outlined in further detail below, the present disclosure describes quinacridone additives that provide large mechanical property enhancement without degradation of other properties of the polymeric material, and, in addition, require low additive loading as compared to currently available additives.

[0028] In an embodiment, the present disclosure relates to additives in a polymer matrix to enhance mechanical properties of the polymer matrix. In a particular embodiment, the additive is a quinacridone additive that provides large mechanical property enhancements without degradation of other properties of the polymeric material. In this particular embodiment, additive loading is low (less than ~1 wt%). In some embodiments, the quinacridone additive can be derived from:

5 , or combinations of the same and like.

[0029] In some embodiments, R can be an alkyl group, an alkoxyl group, an aldehyde, a carboxyl group, COOH, hydrogen, or combinations of the same and like. In various embodiments, R can be ethyl, n-hexyl, n-octyl, n-dodecyl, n-dodecyl, 2-ethyl hexyl, polyisobutylene, or combinations of the same and like. In some embodiments, X can be a halogen. In some embodiments, X can be Br or F.

[0030] In some embodiments, the quinacridone additive can be derived from the aforementioned quinacridone derivatives. In some embodiments, the quinacridone additive has intermolecular hydrogen bonds. In some embodiments, the quinacridone additive does not have intermolecular hydrogen bonds. In an embodiment of the present disclosure, a quinacridone additive with intermolecular hydrogen bonds is C8 IQA:

[0031] In another embodiment of the present disclosure, a quinacridone additive without intermolecular hydrogen bonds is C8-CH₃ IQA:

[0032] The C8 IQA and C8-CH₃ IQA additives were chosen due to their fused-aromatic rigid backbones to maintain the Young’s modulus and long alkyl chains to enable soluble in a polymer matrix.

[0033] In some embodiments, the additives of the present disclosure can enhance fracture toughness and scratching resistance of a polymer matrix. In some embodiments, the additives of the present disclosure provide for simple mixing without covalent linkage with the polymer matrix, and as such, this allows for universal use among many polymers. Furthermore, the additives of the present disclosure provide for easy storage with the polymer.

[0034] In some embodiments, the polymer matrix can include, but is not limited to:

e, polycarbonate, polyamide (nylon), polyimide, laminated glass, polydimethylsiloxane (PDMS), polyester, epoxy, phenolic resin, or combinations thereof. In some embodiments, the polymer matrix further includes various curing agents, such as, for example, a curing agent for an epoxy resin. In some embodiments, the epoxy resin can be DER™ 354 and the curing agent can be W (is a non-methylene dianiline, aromatic amine) which is shown below.

[0035] FIG. 6A and FIG. 6B illustrate the mechanical properties of C8 IQA and C8-CH₃ IQA additives in epoxy. As can be seen in FIG. 6B, strength and elongation increase -15.4% and -55.9%, respectively, for epoxy with C8 IQA while, for epoxy with C8-CH₃ IQA, strength and elongation increase -15.6% and -79.4%, respectively. As shown in FIG. 6A and FIG. 6B, C8 IQA and C8-CH₃ IQA both show large increases in mechanical properties to epoxy while maintaining low additive loading.

[0036] FIG. 7A, FIG. 7B, and Table 3 illustrate that as the C8 IQA and C8-CH₃ IQA content increased in the epoxy, both strength and elongation also increased. Table 3, shown below, illustrates summary results of modulus, tensile strength, and strain at break for neat epoxy, 0.1 wt% C8 in epoxy, 0.2 wt% C8 in epoxy, 0.3 wt% C8 in epoxy, 0.2 wt% C8-CH₃ in epoxy, 0.5 wt% C8-CH₃ in epoxy, and 1 wt% C8-CH₃ in epoxy.

Table 3

Addition Modulus (GPa) Tensile strength (MPa) Strain at Break (%)

Neat Epoxy 2.81 + 0.16 66.2 + 11.2 3.4 + 0.9 0.1% C8 2.73 ± 0.21 73.2 + 5.2 4.4 + 0.7 0.2% C8 2.88 + 0.19 76.0 + 6.1 4.4 + 1.3 0.3% C8 2.95 + 0.15 76.4 + 4.8 5.3 + 1.4 0.2% C8-CH₃ 2.89 + 0.13 71.2 + 7.5 4.2 + 1.2 0.5% C8-CH3 2.84 + 0.17 76.6 + 3.3 5.2 + 0.7 1% C8-CH3 2.83 + 0.10 76.5 + 1.9 6.1 + 0.7

[0037] FIG. 8A illustrates DSC results and FIG. 8B illustrates DMA results of epoxy and epoxy with C8 IQA additives. As can be seen in FIG. 8A, FIG. 8B, and Table 4, shown below, the glass transition temperature is maintained.

Table 4

Sample _ T_g (by DSC) _ T_g (by DMA)

Neat Epoxy 146 °C 143 °C

Epoxy/0.1% C8 IQA 147 °C N/A

Epoxy/0.2% C8 IQA_ 146 °C_ 144 °C

[0038] As shown above, quinacridone additives in a polymeric material allows for improving mechanical properties, such as, elongation and strength without sacrificing other mechanical properties of the polymeric material. The quinacridone additives of the present disclosure have been shown to require a low additive content which allows for a large increase for enhancement of mechanical properties with low loading. Furthermore, the quinacridone additives of the present disclosure can be applied to different polymer matrixes, allow for good appearance (transparent), offer versatile molecular structures to tailor to specific properties, and exhibit a highly feasible ability for processing (no added procedure other than blending).

[0039] Although various embodiments of the present disclosure have been illustrated in the accompanying Drawings and described in the foregoing Detailed Description, it will be understood that the present disclosure is not limited to the embodiments disclosed herein, but is capable of numerous rearrangements, modifications, and substitutions without departing from the spirit of the disclosure as set forth herein.

[0040] The term“substantially” is defined as largely but not necessarily wholly what is specified, as understood by a person of ordinary skill in the art. In any disclosed embodiment, the terms“substantially,”“approximately,”“generally,” and“about” may be substituted with“within [a percentage] of’ what is specified, where the percentage includes 0.1, 1, 5, and 10 percent.

[0041] The foregoing outlines features of several embodiments so that those skilled in the art may better understand the aspects of the disclosure. Those skilled in the art should appreciate that they may readily use the disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the disclosure, and that they may make various changes, substitutions, and alterations herein without departing from the spirit and scope of the disclosure. The scope of the invention should be determined only by the language of the claims that follow. The term“comprising” within the claims is intended to mean“including at least” such that the recited listing of elements in a claim are an open group. The terms“a,”“an,” and other singular terms are intended to include the plural forms thereof unless specifically excluded.

Claims

CLAIMS What is claimed is:

1. A composition comprising a polymer matrix and an additive, wherein the additive is a quinacridone additive.

2. The composition of claim 1, wherein the quinacridone additive is derived from a compound selected from the group consisting of:

, or combinations thereof.

3. The composition of claim 2, wherein each R is selected from the group consisting of an alkyl group, an alkoxyl group, an aldehyde, a carboxyl group, COOH, hydrogen, or combinations thereof.

4. The composition of claim 2, wherein each R is selected from the group consisting of ethyl, n-hexyl, n-octyl, n-dodecyl, n-dodecyl, 2-ethyl hexyl, polyisobutylene, or combinations thereof.

5. The composition of claim 2, wherein each X is a halogen.

6. The composition of claim 2, wherein each X is selected from the group consisting of Br, F, or combinations thereof.

7. The composition of claim 1, wherein the quinacridone additive is selected from the group consisting of:

, or combinations thereof.

8. The composition of claim 1, wherein the polymer matrix is selected from the group consisting of:

rbonate, polyamide (nylon), polyimide, laminated glass, polydimethylsiloxane (PDMS), polyester, epoxy, phenolic resin, or combinations thereof.

9. The composition of claim 1, wherein the additive is present in an amount at or below about 1 wt%.

10. A method of making a composition comprising adding an additive to a polymer matrix, wherein the additive is a quinacridone additive.

11. The method of claim 10, wherein the quinacridone additive is derived from a compound selected from the group consisting of:

, or combinations thereof.

12. The method of claim 11, wherein each R is selected from the group consisting of an alkyl group, an alkoxyl group, an aldehyde, a carboxyl group, COOH, hydrogen, or combinations thereof.

13. The method of claim 11, wherein each R is selected from the group consisting of ethyl, n-hexyl, n-octyl, n-dodecyl, n-dodecyl, 2-ethyl hexyl, polyisobutylene, or combinations thereof.

14. The method of claim 11, wherein each X is a halogen.

15. The method of claim 11, wherein each X is selected from the group consisting of Br, F, or combinations thereof.

16. The method of claim 10, wherein the quinacridone additive is selected from the group consisting of:

, or combinations thereof.

17. The method of claim 10, wherein the polymer matrix is selected from the group consisting of:

, polyurethane, polycarbonate, polyamide

(nylon), polyimide, laminated glass, polydimethylsiloxane (PDMS), polyester, epoxy, phenolic resin, or combinations thereof.

18. The method of claim 10, wherein the additive is present in an amount at or below about 1 wt%.

19. A composition comprising a polymer matrix and an additive, wherein the additive is a quinacridone additive selected from the group consisting of:

, or combinations thereof; and

wherein the additive is present in an amount at or below about 1 wt%.

20. A method of making a composition comprising adding an additive to a polymer matrix, wherein the additive is a quinacridone additive selected from the group consisting of:

, or combinations thereof; and wherein the additive is present in an amount at or below about 1 wt%.