阅读说明：本技术 粘合异种材料的方法和制剂 (Method and formulation for bonding dissimilar materials ) 是由 泽赫拉·塞温奇 迪·达塔什维利 孟凡卿 吴尚仁 钦努·布拉哈特厄斯瓦兰 于 2019-09-18 设计创作，主要内容包括：本公开涉及胶合剂的制剂和粘合异种材料的方法。所述制剂和方法可以将含有非晶态或具有低结晶度的第一聚烯烃的非聚氯乙烯(PVC)粘合到为刚性材料或硬质PVC的第二材料。所述方法和制剂可以通过在界面处共溶解或在粘合之前活化一种材料来起作用。(The present disclosure relates to a formulation of a glue and a method of bonding dissimilar materials. The formulations and methods may bond a non-polyvinyl chloride (PVC) containing a first polyolefin that is amorphous or has low crystallinity to a second material that is a rigid material or a rigid PVC. The methods and formulations may function by co-dissolving at the interface or activating a material prior to bonding.)

1. A method of bonding a first material to a second material with an adhesive, the first and second materials being dissimilar, wherein

The first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in the range of about 0.1% to about 50% crystallinity;

the second material comprises a rigid amorphous material having a tensile modulus of about 1800 to about 3000MPa, PVC having a shore a hardness of about 70 to about 85, or a combination thereof; and is

The adhesive comprises an ethylene vinyl acetate copolymer, a polyolefin elastomer, a tackifier, and a solvent;

the method includes applying an adhesive to form a bond between the first material and the second material.

2. The method of claim 1, wherein the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO).

3. The method of claim 1 or 2, further comprising sterilizing the first and second materials at a temperature in the range of about 40 ℃ to about 60 ℃ after applying the adhesive.

4. The method of claim 1 or 2, wherein the rigid amorphous material comprises polycarbonate or a copolymer thereof or polyacrylate or a copolymer thereof.

5. A method of bonding a first material to a second material, the first and second materials being dissimilar, wherein

The first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in the range of about 0.1% to about 50% crystallinity;

the second material comprises a rigid amorphous material having a tensile modulus of about 1800 to about 3000MPa, PVC having a shore a hardness of about 70 to about 85, or a combination thereof;

the method comprises the following steps:

i.) modifying the first material with polar functional groups that increase the affinity of the first material for the second material;

ii.) bonding the first material to the second material.

6. The method of claim 5, wherein modifying the first material comprises grafting polar functional groups to the first material via reactive extrusion.

7. The method of claim 6, wherein the polar functional group is formed by reaction with a monomeric compound comprising at least one ester group.

8. The method of claim 7, wherein the monomeric compound comprises a carbon-carbon double bond capable of reacting with an activating material.

9. A method of bonding a first material to a second material, the first and second materials being dissimilar, wherein

The first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in the range of about 0.1% to about 50% crystallinity;

the second material comprises a rigid amorphous material having a tensile modulus of about 1800 to about 3000MPa, PVC having a shore a hardness of about 70 to about 85, or a combination thereof;

the method comprises the following steps:

i.) providing an adhesive comprising one or more of the group consisting of:

a.) an organic solvent or solvent mixture capable of dissolving the first material and the second material;

b.) a blend of a first material and a second material;

c.) a polymeric material selected from polypropylene (PP), thermoplastic olefin (TPO) and thermoelastic elastomer (TPE), said polymeric material being functionalized with polar groups;

ii.) bonding the first material to the second material using an adhesive.

10. The method of claim 9, wherein the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO).

11. The method of claim 9 or 10, wherein the rigid amorphous material comprises polycarbonate or a copolymer thereof or polyacrylate or a copolymer thereof.

12. The method of claim 9 or 10, wherein the polar group is selected from the group consisting of: a maleic anhydride group; a glycidyl methacrylate group; an N-substituted maleimide group; a carboxylic acid-containing group selected from the group consisting of fumaric acid groups, citraconic acid groups, and itaconic acid groups, or an ester, amide, imide, or anhydride thereof.

13. A method of bonding a first material to a second material, the first and second materials being dissimilar, wherein

The first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in the range of about 0.1% to about 50% crystallinity;

the second material comprises a rigid amorphous material having a tensile modulus of about 1800 to about 3000MPa, PVC having a shore a hardness of about 70 to about 85, or a combination thereof;

the method comprises the following steps:

i.) modifying the first material using any one from the group consisting of:

a.) mixing a first material with up to about 51 wt% of a functionalized polymer;

b.) mixing the first material with up to about 5 wt% of a second compatibilizer;

c) mixing the first material with up to about 5 wt% of an adhesion promoter;

d.) mixing the first material with up to about 5 wt% of an ethylene acrylic acid copolymer; and

ii.) bonding the modified first material to the second material.

14. The method of claim 13, wherein the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO).

15. The method of claim 13 or 14, wherein the functionalized polymer is selected from the group consisting of: maleic Anhydride (MAH) modified polypropylene copolymer or homopolymer, MAH modified polyolefin elastomer or plastomer, ethylene acrylate-maleic anhydride terpolymer, methacrylate grafted on olefin copolymer, MAH functionalized Styrene Ethylene Butylene Styrene (SEBS) and linear triblock 13% styrene ethylene butylene 30% styrene copolymer.

16. The method of claim 13 or 14, wherein the adhesion promoter is a tackifier or EVA.

17. A method of bonding a first material to a second material, the first and second materials being dissimilar, wherein

The first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in the range of about 0.1% to about 50% crystallinity;

the second material comprises a rigid amorphous material having a tensile modulus of about 1800 to about 3000MPa, PVC having a shore a hardness of about 70 to about 85, or a combination thereof;

the method comprises the following steps:

i.) providing an adhesive comprising a solvent-free polymeric material;

ii) melting the binder;

iii.) bonding the first material to the second material using a molten adhesive.

18. The method of claim 17, wherein the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO).

19. The method of claim 17 or 18, wherein the adhesive further comprises a tackifier.

20. The method of claim 17 or 18, wherein the solvent-free polymeric material is Ethylene Vinyl Acetate (EVA), maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted plastomer, thermoplastic polyurethane and hydrogenated styrene block copolymer.

Technical Field

The present disclosure relates to the field of polymeric materials. More particularly, the present disclosure relates to dissimilar polymeric materials and adhesives or adhesive formulations for bonding thereof.

Background

Various grafting techniques for increasing the surface energy or for making dissimilar materials compatible are known in the prior art [1, 2,4,6, 7, 9, 10 ]. Due to the chemical differences, bonding dissimilar materials is difficult to achieve. In particular, bonding polyolefin-based materials is challenging due to the low surface energy, which requires primer coating with adhesives or special surface treatments prior to bonding. The prior art includes examples of modification techniques or grafting, as well as specific formulations for improving the adhesion between functionalized polyolefins and various coatings, paints and adhesives [3, 5, 11 ].

In particular, EP 1233039 describes a modified polyolefin formulation (based on thermoplastic olefins) comprising grafting functional groups with one ester group and at least one hydroxyl group and/or one ethylene oxide group to improve adhesion to coatings and adhesives. It is known in the industry to use cements and primers to join polyvinyl chloride (PVC) pipes and pipe fittings. For example, U.S. patent No. 6613187B1 describes a glue technique for adhering polyolefin materials to each other or similar materials and low crystalline polymers to low crystalline polymers. However, this disclosure does not describe a method or formulation to achieve the adhesion of dissimilar materials having different chemical and material properties (e.g., crystallinity, polarity, etc.).

Disclosure of Invention

The techniques disclosed herein can advantageously achieve higher graft densities compared to commercially available grafted polyolefins (typically up to 1 wt%). Moreover, the techniques herein may eliminate the need for a primer and the additional step of applying it, as well as the use of expensive adhesives prior to attaching the dissimilar materials. Advantageously, common and inexpensive solvents can be used to join parts suitable for high volume manufacturing or part assembly. Additional advantages may include minimal changes in the bulk properties of the assembled parts, such as clarity and suitability for medical delivery (e.g., low extractables/leachables) applications.

In addition, the methods described herein involve the challenge of bonding dissimilar polymeric materials. In particular, these methods are configured to improve the adhesion between low crystalline polyolefins (thermoplastic elastomers, thermoplastic olefins, etc.) and rigid amorphous materials or low crystalline polyvinyl chloride (PVC). In addition, the disclosed method allows the use of inexpensive solvents that are practical for use in high volume manufacturing, avoiding separate primer application or heating steps. Although specific examples of use include the medical industry, these solutions have broad application potential in other industries as well.

In one embodiment, an adhesive for adhering a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range from about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; and the adhesive comprises one or more polymers, for example, ethylene vinyl acetate copolymers, polyolefin elastomers, which may be up to 51 wt% or more, and a solvent or solvent set forming a solvent system, and optionally a tackifier. The adhesive is used to bond dissimilar materials when exposed to heat using conventional sterilization methods.

In another embodiment, a method of bonding a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range of about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; the method comprises the following steps: i.) modifying the first material with polar functional groups that increase the affinity of the first material for the second material; and ii) bonding the first material to the second material. The method improves the chemical affinity of the base non-PVC material for the second material by modifying it with highly polar functional groups and its ability to chemically bond through a suitable solvent or solvent system.

In another embodiment, a method of bonding a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range of about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; the method comprises the following steps: i.) providing an adhesive comprising one or more of the group consisting of: a.) an organic solvent or solvent mixture capable of dissolving the first material and the second material; b.) a mixture of a first material and a second material; c.) a polymeric material selected from polypropylene (PP), thermoplastic olefin (TPO) and thermoplastic elastomer (TPE), said polymeric material being functionalized with polar groups; and ii) bonding the first material to the second material using an adhesive.

In another embodiment, a method of bonding a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range of about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; the method comprises the following steps: i.) modifying the first material using at least one technique selected from the group consisting of: a.) mixing a first material with up to about 51 wt% of a functionalized polymer; b.) mixing the first material with up to about 5 wt% of a second compatibilizer; c) mixing the first material with up to about 5 wt% of an adhesion promoter; d.) mixing the first material with up to about 5 wt% of an ethylene acrylic acid copolymer; and ii) bonding the modified first material to the second material.

Related aspects include the use of other methods that encompass similar technical principles. For example, surface deposition techniques can be used to graft functional groups to increase polarity, thereby increasing the polarity of the non-PVC material. One example includes the use of atmospheric plasma deposition techniques to deposit polar chemical groups, such as maleic anhydride, acrylic acid, or similar agents, on non-PVC surfaces. The technology can modify the non-PVC surface while maintaining the bulk properties (rheological property, mechanical properties, transparency, etc.) required by the material. The methods disclosed herein may also be optimized for processing via conventional processing equipment.

Additional features and advantages of the subject technology will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the subject technology. The advantages of the subject technology will be realized and attained by the structure particularly pointed out in the written description and embodiments thereof as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the subject technology.

Drawings

Various features of illustrative embodiments of the invention are described below with reference to the drawings. The illustrated embodiments are intended to illustrate, but not to limit the invention. The drawings contain the following figures:

FIG. 1 shows the use as described in example 1A functionalized olefin copolymer bonded Luer-tubing assembly.

Figure 2 shows the adhesion testing apparatus and sample placement therein as described in example 1.

FIG. 3 shows a T-shaped polycarbonate joint made of 50/50Makrolon2458/Makrolon Rx1805 bonded to a thermoplastic elastomer tube made of Teknor Apex Medialst MD575 according to the method of example 2.

Fig. 4 shows a graph of the average bonding tension load for different concentrations of OFS6030 solution in the experiment of example 2.

Figure 5 shows a graph of adhesion as a function of oven temperature for the material in example 1.

FIG. 6 is a graph of the affinity under certain components in the adhesive.

Detailed Description

It will be appreciated that various configurations of the subject technology will become apparent to those skilled in the art from this disclosure, wherein various configurations of the subject technology are shown and described by way of example. As will be realized, the subject technology is capable of other and different configurations and its several details are capable of modification in various other respects, all without departing from the scope of the subject technology. Accordingly, the summary, drawings, and detailed description are to be regarded as illustrative in nature and not as restrictive.

The detailed description set forth below is intended as a description of various configurations of the subject technology and is not intended to represent the only configurations in which the subject technology may be practiced. The accompanying drawings are incorporated herein and constitute a part of the detailed description. The detailed description includes specific details for the purpose of providing a thorough understanding of the subject technology. It will be apparent, however, to one skilled in the art that the subject technology may be practiced without these specific details. In some instances, well-known structures and elements are shown in block diagram form in order to avoid obscuring the concepts of the subject technology. Similar elements are labeled with the same element numbers for ease of understanding.

In one embodiment, an adhesive for adhering a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range from about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; and the adhesive comprises one or more polymers, for example, ethylene vinyl acetate copolymers, polyolefin elastomers, which may be up to 51 wt% or more, and a solvent or solvent set forming a solvent system, and optionally a tackifier.

The crystallinity of a solid material, such as a polymer solid, may be determined by any suitable means. "crystallinity" refers to the structural order of a solid. In a crystal, atoms or molecules are arranged in a regular, periodic manner. Crystallinity will affect the hardness, density and transparency of the solid. The order of crystalline materials can be understood by comparing the position of atoms in the gaseous state, where the relative position of atoms or molecules is completely random. "amorphous" materials (e.g., liquids and glasses) represent an intermediate case with order over short distances (a few atoms or molecular spacings) and no order over long distances.

Some polymeric materials can be prepared in a manner that produces a mixture of crystalline and amorphous regions. In such cases, crystallinity is typically specified as a volume percentage of crystalline material. Crystallization of a polymer is a process related to the partial arrangement of its molecular chains. These chains fold together to form ordered regions called platelets, which constitute a larger spherical structure called spherulites.https://en.wikipedia.org/wiki/Crystallization_of_polymers-cite_note- sp-1. The polymer can be meltedCrystallization upon bulk cooling, mechanical stretching or solvent evaporation. Crystallization affects the optical, mechanical, thermal and chemical properties of polymers. The degree of crystallinity is estimated by different analytical methods, generally between 10% and 80%, so that crystalline polymers are generally referred to as "semi-crystalline". The properties of semi-crystalline polymers depend not only on the degree of crystallinity but also on the size and orientation of the molecular chains.

One technique for determining the crystallinity of polymer solids is Differential Scanning Calorimetry (DSC). DSC is a technique that measures heat flow into or out of a material as a function of time or temperature. The crystallinity of the polymer can be quantified by DSC by melting (melting,. DELTA.H) with the polymer_Melting) The relative heat. The heat of fusion observed is reported as percent crystallinity by normalizing it to that of a 100% crystalline sample of the same polymer. Since there are few real samples of 100% crystalline polymer, literature values are often used as the value. In some embodiments, the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer characterized by DSC at a 10 ℃/min rate having a heat of fusion, when combined with a DSC melting peak, of less than about 59J/g. In some embodiments, the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer having a heat of fusion, as characterized by DSC, of less than about 23J/g.

In some embodiments, the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer having a crystallinity of from about 0.1% to about 50%, from about 1% to about 45%, from about 5% to about 40%, from about 10% to about 30%, from about 1% to about 30%, and from about 5% to about 25% crystallinity.

The second material comprises a rigid amorphous material having a tensile modulus of about 1800 to about 3000MPa, PVC having a shore a hardness of about 70 to about 85, or a combination thereof. One of ordinary skill in the art will recognize how to determine the tensile modulus or shore a hardness. Tensile modulus is a mechanical property that measures the stiffness of a solid material. It defines the relationship between stress (force per unit area) and strain (proportional deformation) in a material in the linear elastic state of uniaxial deformation. When a small load is applied to the solid material during compression or extension, the solid material will elastically deform. The elastic deformation is reversible (after removal of the load, the material returns to its original shape).

In the case of near zero stress and strain, the stress-strain curve is linear and the relationship between stress and strain is described by hooke's law, which states that stress is proportional to strain. The proportionality coefficient is the tensile modulus. The higher the modulus, the greater the stress required to produce the same amount of strain; an ideal rigid body would have an infinite tensile modulus. Mathematically, the tensile modulus can be expressed as: e ═ σ/∈, where E is the tensile modulus (usually expressed in Pa, kPa, or MPa), σ is the uniaxial stress or force per unit surface, and ∈ is the strain or proportional deformation (change in length divided by the original length) (dimensionless).

Hardness is typically measured using a shore durometer. The higher the number on the shore scale, the greater the indentation resistance of the material and therefore the harder the material, while the lower the number, the smaller and softer the indentation resistance. There are several scales for hardness gauges used with materials having different properties. The two most common scales using slightly different measurement systems are the ASTM D2240 type a and type D scales. Like many other hardness tests, a durometer measures the depth of a material indentation produced by a given force on a standard presser foot. The depth depends on the hardness of the material, its viscoelasticity, the shape of the presser foot and the duration of the test. The ASTM D2240 durometer can measure the initial hardness or the indentation hardness after a given time. The basic test requires that the force be applied in a consistent manner, without impact, and the hardness (indentation depth) be measured. If timed firmness is required, force is applied at the desired time and then read. The values on the scale are between 0 and 100. Materials characterized herein by hardness are measured on the ASTM D2240 scale.

In some embodiments, the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO). In some embodiments, the rigid amorphous material comprises polycarbonate or a copolymer thereof, polyacrylate or a copolymer thereof, such as a methyl methacrylate-acrylonitrile-butadiene-styrene (mABS) copolymer, or acrylonitrile-butadiene-styrene (ABS) or a copolymer thereof, or a derivative of any of the above. Throughout this disclosure, the term "derivative" includes, but is not limited to, the indicated ester, amide, imide, or anhydride having the structure of the derivative.

In some embodiments, the solvent or solvent system is configured to be applied via a solvent dispenser, dip coating, or manual application. Suitable solvents or solvent systems for use in the present disclosure include, but are not limited to, solvents or solvent combinations comprising: cyclohexanone, methyl ethyl ketone, cyclohexane, ethyl acetate, isobutyl acetate, n-butyl acetate, methyl isobutyl ketone, tetrahydrofuran, heptane, and any combination thereof.

In some embodiments, the adhesive is stable to sterilization processing temperatures up to about 60 ℃.

In some embodiments, the adhesive further comprises up to 5 wt% of an organosol-modified polypropylene dispersion, up to 3 wt% of one or more tackifiers, or both. Suitable tackifiers include, but are not limited to, terpene phenols, styrenated terpenes, rosin esters, terpene resins, and hydrocarbon resins.

In some embodiments, a method is provided that includes applying an adhesive to form a bond between a first material and a second material. Application of the adhesive may include application by a solvent dispenser, dip coating, or manual application. After the adhesive is applied, the adhesive system may be sterilized at a temperature in the range of about 40 ℃ to about 60 ℃, which may help the adhesive cure and enhance the adhesion.

In a second embodiment, a method of bonding a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range from about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; the method comprises the following steps: i.) modifying the first material with polar functional groups that increase the affinity of the first material for the second material; and ii) bonding the first material to the second material. In the method of this embodiment, the first material and the second material may have the same characteristics as the materials described above in the adhesive embodiment.

In some embodiments, the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO). In some embodiments, the rigid amorphous material comprises polycarbonate or a copolymer thereof, polyacrylate or a copolymer thereof, such as a methyl methacrylate-acrylonitrile-butadiene-styrene (mABS) copolymer, or acrylonitrile-butadiene-styrene (ABS) or a copolymer thereof, or a derivative of any of the above.

In some embodiments, the first material is modified by grafting a polar functional group to the first material via reactive extrusion. In some embodiments, reactive extrusion includes first activating a first material with an initiator to provide an activated material. An "initiator" is a reagent that can generate free radical species and promote free radical reactions under mild conditions. These substances generally have weak bonds with less bond dissociation energy. Examples include halogen molecules, azo compounds, and organic and inorganic peroxides. In some embodiments, the initiator is a peroxide. In some embodiments, the initiator is selected from benzyl peroxide, dicumyl peroxide, or 2,2' -azobisisobutyronitrile.

In some embodiments, the polar functional group is formed by reaction with a monomeric compound comprising at least one ester group. In some embodiments, the monomeric compound comprises a carbon-carbon double bond capable of reacting with the activating material. In some embodiments, the monomer compound is selected from the group consisting of methyl methacrylate, glycidyl methacrylate, and vinyl acetate.

In some embodiments, reactive extrusion is performed in a molten state of the first material.

In some embodiments, modifying the first material comprises grafting a monomer compound comprising a polar functional group to the first material using one or more adhesion promoters. Suitable tackifiers are described above. In some embodiments, the one or more tackifiers are selected from terpene phenols, styrenated terpenes, rosin esters, terpene resins, and hydrocarbon resins.

In some embodiments, the monomeric compound comprises isoprene having a carbon-carbon double bond capable of reacting with the activating material.

In some embodiments, the method further comprises bonding the modifying material to the second material by dissolution at the interface as a result of the solvent or solvent system. In some embodiments, the solvent or solvent system comprises a solvent selected from the group consisting of: cyclohexanone, methyl ethyl ketone, cyclohexane, ethyl acetate, isobutyl acetate, n-butyl acetate, methyl isobutyl ketone, tetrahydrofuran, heptane, and any combination thereof.

In some embodiments, modifying the first material further comprises combining with up to about 10 wt% of a second compatibilizer selected from polyetheramine, Ethylene Vinyl Acetate (EVA), or both, wherein the second compatibilizer increases the polarity of the first material. In some embodiments, the modified first material further comprises a combination with up to about 10 wt% of a isoprenyl tackifier. In some embodiments, the isoprenyl tackifier is a terpene.

In some embodiments, modifying the first material further comprises combining with up to about 1 wt% of an antioxidant, up to about 1 wt% of a processing aid, or both. In some embodiments, the antioxidant is pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) or 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene. In some embodiments, the processing aid is selected from fatty acid amide slip agents and inorganic mineral anti-caking agents.

In another embodiment, a method of bonding a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range of about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; the method comprises the following steps: i.) providing an adhesive comprising one or more of the group consisting of: a.) an organic solvent or solvent mixture capable of dissolving the first material and the second material; b.) a mixture of a first material and a second material; c.) a polymeric material selected from polypropylene (PP), thermoplastic olefin (TPO) and thermoelastic elastomer (TPE), said polymeric material being functionalized with polar groups; and ii) bonding the first material to the second material using an adhesive. The materials used in this method may be the same as those described in the above embodiments.

In some embodiments, the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO). In some embodiments, the rigid amorphous material comprises polycarbonate or a copolymer thereof, polyacrylate or a copolymer thereof, such as a methyl methacrylate-acrylonitrile-butadiene-styrene (mABS) copolymer, or acrylonitrile-butadiene-styrene (ABS) or a copolymer thereof, or a derivative of any of the above.

In some embodiments, the polar group is selected from the group consisting of: a maleic anhydride group; a glycidyl methacrylate group; an N-substituted maleimide group; a carboxylic acid-containing group selected from the group consisting of fumaric acid groups, citraconic acid groups, and itaconic acid groups, or an ester, amide, imide, or anhydride thereof.

In some embodiments, the adhesive comprises up to about 5 wt% of the second compatibilizer. In some embodiments, the second compatibilizer is a polyetheramine. In some embodiments, the adhesive comprises from about 3.4 to about 51 wt% of a solvent or solvent mixture comprising polar and non-polar solvents. In some embodiments, the polar solvent is selected from Methyl Ethyl Ketone (MEK), cyclohexanone, and dichloromethane, and the non-polar solvent is selected from hexane and heptane.

In some embodiments, the adhesive further comprises an additional ingredient selected from the group consisting of: up to about 5 wt% of an adhesion promoter; up to about 2 wt% of a wetting agent; up to about 1 wt% of a hydrolyzing agent; up to about 5 wt% of an expandable monomer compound; and up to about 5 wt% of a polymer selected from the group consisting of polyurethane, styrene butadiene rubber having a vinyl content of greater than 10%, and Ethylene Vinyl Acetate (EVA).

In some embodiments, the adhesion promoter is a tackifier selected from the group consisting of rosin, hydrocarbon resins, and terpene resins. In some embodiments, the wetting agent is a functional silane. In some embodiments, the swellable monomer is a lactone. In some embodiments, the lactone is glucono delta-lactone.

In another embodiment, a method of bonding a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range of about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; the method comprises the following steps: i.) modifying the first material using at least one technique selected from the group consisting of: a.) mixing a first material with up to about 51 wt% of a functionalized polymer; b.) mixing the first material with up to about 5 wt% of a second compatibilizer; c) mixing the first material with up to about 5 wt% of an adhesion promoter; d.) mixing the first material with up to about 5 wt% of an ethylene acrylic acid copolymer; and ii) bonding the modified first material to the second material. The materials used in this method may be the same as described above for the other embodiments.

In some embodiments, the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO). In some embodiments, the rigid amorphous material comprises polycarbonate or a copolymer thereof, polyacrylate or a copolymer thereof, such as a methyl methacrylate-acrylonitrile-butadiene-styrene (mABS) copolymer, or acrylonitrile-butadiene-styrene (ABS) or a copolymer thereof, or a derivative of any of the above.

In some embodiments, the functionalized polymer is selected from the group consisting of: maleic Anhydride (MAH) modified polypropylene copolymer or homopolymer, MAH modified polyolefin elastomer or plastomer, ethylene acrylate-maleic anhydride terpolymer, methacrylate grafted on olefin copolymer, MAH functionalized styrene ethylene butylene styrene (ses) and linear triblock 13% styrene ethylene butylene 30% styrene copolymer. In some embodiments, the functionalized polymer is a polyetheramine.

In some embodiments, the adhesion promoter is a tackifier or EVA.

In some embodiments, the modified material is formulated to optimize processing by conventional processing equipment while retaining the bulk properties (e.g., molecular weight, crystallinity, dispersibility, molecular structure, hardness, tensile modulus, etc.) of the modified material.

In another embodiment, a method of bonding a first material to a second material, the first material and the second material being dissimilar, wherein the first material comprises a non-polyvinyl chloride (non-PVC) polyolefin polymer, wherein the non-PVC polyolefin polymer is amorphous or has a crystallinity in a range of about 0.1% to about 50% crystallinity; the second material comprises a rigid amorphous material having a tensile modulus in the range of about 1800 to about 3000MPa, a PVC having a shore a hardness in the range of about 70 to about 85, or a combination thereof; the method comprises the following steps: i.) providing an adhesive comprising a solvent-free polymeric material; ii) melting the binder; and iii) bonding the first material to the second material using a molten adhesive. The materials used in this method may be the same as those used in the above-described embodiments.

In some embodiments, the non-PVC polyolefin polymer is a styrene-based thermoplastic elastomer (TPE) or a styrene-based thermoplastic olefin (TPO). In some embodiments, the rigid amorphous material comprises polycarbonate or a copolymer thereof, polyacrylate or a copolymer thereof, such as a methyl methacrylate-acrylonitrile-butadiene-styrene (mABS) copolymer, or acrylonitrile-butadiene-styrene (ABS) or a copolymer thereof, or a derivative of any of the above. In some embodiments, the adhesive further comprises a tackifier. In some embodiments, the solventless polymeric material is Ethylene Vinyl Acetate (EVA), maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted plastomer, thermoplastic polyurethane, and hydrogenated styrene block copolymer.

Examples

Example 1

Is a methacrylate grafted onto an olefin copolymer dispersed in an organic solvent. Can be used as obtainedAnd coated directly onto the tube with a cotton swab or diluted in cyclohexanone solvent and then coated onto the tube. The adhesion method to PVC was tested using a Luer assembly. The adhesion was measured using a mechanical tester equipped with a 500N load cell, maintaining a 0.25 inch gap between the jaws and the adapter of the luer. The results are shown in Table 1. Fig. 1 shows the assembled luer and hose (hosing). The test speed was 1 inch/min. The force was measured using a 500N load cell in the Instron (model 5500Q 1979). Fig. 2 shows the test device and the assembled luer and hose placed therein.

TABLE 1And adhesion results of solvent test

Calculated

Example 2

Use of the Xiameter from Dow Corning^TMSilane wetting agents improve the adhesion between thermoplastic elastomer tubes made by Teknor Apex Medialst MD575 and T-type polycarbonate connectors made by 50/50Makrolon2458/Makrolon Rx 1805. The different types of silane reagents used are listed in table 2. Then, as followsStep (c), the strength of the bond was evaluated.

TABLE 2 silane reagents for the experiments

Example 3

In the experiment, 10ml of Tetrahydrofuran (THF) was injected into a 20ml glass vial. Acetic acid, 15 μ l, was added to accelerate hydrolysis of the reagent. An aliquot of the silane coupling agent was poured into the solution and mixed for 5 minutes to ensure hydrolysis was complete. The tube was immersed in the solution, gently agitated and removed after 1 to 2 minutes. The tube is then inserted into the fitting. Fig. 3 shows one embodiment of an assembled sample. These samples were stored for two days to allow curing to complete.

The samples were then treated with a simulated oxirane (oxetane) by heating at 60 c, 30% relative humidity for 5 hours. The samples were then stored at room temperature for 5 days. The samples were subjected to an Instron test at a vehicle speed (train rate) of 254mm/min to record the maximum load before failure. In the experiments, a 2% strength by volume silane solution was tested. Tables 3 and 4 summarize data showing statistically significant increases in adhesion using OFS6020, OFS6030, and OFS 6300. The average tensile strength of the different silanes is shown in figure 4.

Table 3 adhesion data using silane wetting agents

TABLE 4 statistical significance of wetting agent on adhesion

Example 3-a heat aging study was conducted to understand the effect of typical sterilization process conditions on adhesion. The same materials as in example 1 were used, but with other variationsAmounts such as dilution, diluent or solvent type, tank temperature and heating time. Obtained from Evonik diluted with methyl isobutyl ketone or cyclohexanone in the volume ratios described in Table 1VP 4322E and 4294E. The Degalan solution was applied to the outer surface of the tube with cotton wrapped swabs. mABS for tube2802TR the luer fitting is assembled manually. The samples were placed in an oven set at 32 ℃ and 55 ℃ for 1 to 6 days. The same mechanical tester and tensile testing conditions as in example 1 were used. The results show that the adhesion increases as a function of the oven temperature. The heating time,% dilution or type of diluent did not produce statistically significant changes in adhesion.

TABLE 5 dilution volume ratio

Diluting to percent	Degalan volume	Volume of solvent used for dilution
			Diluting by 0%	10cc	NA
Diluting by 30 percent	10cc	3cc
			Diluting by 60 percent	10cc	6cc

TABLE 6 Heat Effect

Heat for 1 to 6 days.

Example 4

Example 4 Regalite from Eastman^TMR1100 tackifying Hydrocarbon resin DuPont^TM 150 (which is an ethylene-vinyl acetate copolymer or an EVA resin), Dupont AFFINITY^TMGA 1900 polyolefin elastomer (POE) and various formulations were prepared in different ratios as shown in table 7. AFFINITY^TMGA 1900 represents a functionalized polyolefin with maleic anhydride grafting and a melt flow index of 1000g/10min (according to the supplier) at 190 ℃ and 2.16kg of test conditions. The formulation was dissolved in Cyclohexanone (CHN) and Dichloroethane (DCN). The formulation was applied to the outer surface of the tube with a cotton-wrapped cotton swab. Tube composed of mABS2802TR and Y-site (Y-site) made of CYRO GS90 acrylic acid multipolymer. According to table 7, some samples were placed in an oven set at 60 ℃ for 15 hours. The same mechanical tester and tensile testing conditions as in example 1 were used. Table 7 shows that the formulations with POE show an adhesion increase of up to 3 wt%. When POE composition was equal to or greater than 5 wt%, adhesion decreased and variation increased, fig. 6. In addition to the POE composition shown in figure 6, these formulations contained 0.5% Elvax150, 0.1% R1100, and the balance equal wt% CHN and DCN. The results in table 7 also show that the C5 formulation containing tackifier R1100 increased adhesion upon heating at 60 ℃ (representative of sterilization process conditions).

Table 7 experimental design of POE formulations

Further consider

In some embodiments, any clause herein may be dependent on any one of the independent clauses or any one of the dependent clauses. In an aspect, any clause (e.g., dependent or independent clause) may be combined with any other clause or clauses (e.g., dependent or independent clauses). In one aspect, a claim may include some or all of the words (e.g., steps, operations, devices, or components) recited in a clause, sentence, phrase, or paragraph. In one aspect, a claim may include some or all of the words recited in one or more clauses, sentences, phrases or paragraphs. In an aspect, some words in each of the clauses, sentences, phrases, or paragraphs may be removed. In an aspect, additional words or elements may be added to a clause, sentence, phrase, or paragraph. In one aspect, the subject technology may be implemented without utilizing certain components, elements, functions or operations described herein. In an aspect, the subject technology may be implemented with additional components, elements, functions or operations.

The previous description is provided to enable any person skilled in the art to practice the various configurations described herein. While the subject technology has been described in detail with reference to various figures and configurations, it is to be understood that these are for purposes of illustration only and are not to be construed as limiting the scope of the subject technology.

Many other ways are possible to implement the subject technology. The various functions and elements described herein may be divided differently than those shown without departing from the scope of the subject technology. Various modifications to these configurations will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other configurations. Accordingly, many changes and modifications may be made to the subject technology by one of ordinary skill in the art without departing from the scope of the subject technology.

It should be understood that the specific order or hierarchy of steps in the processes disclosed is an illustration of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the processes may be rearranged. Some steps may be performed simultaneously. The accompanying method claims present elements of the various steps in a sample order, and are not meant to be limited to the specific order or hierarchy presented.

As used herein, the phrase "at least one of" preceding a series of items (separating any one item by the term "and" or ") modifies the entire list rather than every member of the list (i.e., every item). The phrase "at least one" does not require the selection of at least one of each of the listed items; rather, the phrase has the meaning including at least one of any one of the items, and/or at least one of any combination of the items, and/or at least one of each item. For example, the phrases "at least one of A, B and C" or "at least one of A, B or C" each refer to a alone, B alone, or C alone; A. any combination of B and C; and/or A, B and C.

Furthermore, to the extent that the terms "includes," "has," "having," "including," "has," "having," "contains," "containing," or the like are used in either the detailed description or the claims, such terms are intended to be inclusive in a manner similar to the term "comprising" as "comprising" is interpreted when employed as a transitional word in a claim.

In one or more aspects, the terms "about," "substantially," and "approximately" can provide an industry-accepted tolerance of relativity between their respective terms and/or items, e.g., from less than one percent to five percent.

The word "exemplary" is used herein to mean "serving as an example, instance, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.

Reference to an element in the singular is not intended to mean "one and only one" unless specifically so stated, but rather "one or more. Pronouns in the male (e.g., his) include the female and neutral gender (e.g., her and its), and vice versa. The term "some" refers to one or more. Underlined and/or italicized headings and subheadings are used for convenience only, do not limit the subject technology, and are not meant to be relevant to an explanation of the description of the subject technology. All structural and functional equivalents to the various elements of the configurations described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the subject technology. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the above description.

Although the detailed description contains many specifics, these specifics should not be construed as limiting the scope of the subject technology, but merely as illustrating different examples and aspects of the subject technology. It should be understood that the scope of the subject technology includes other embodiments not discussed in detail above. Various other modifications, changes, and variations may be made in the arrangement, operation, and details of the methods and apparatus of the subject technology disclosed herein without departing from the scope of the disclosure. Unless otherwise indicated, reference to an element in the singular is not intended to mean "one and only one" unless explicitly so stated, but rather "one or more. Moreover, it is not necessary for a device or method to address each and every problem sought to be solved (or to have each and every advantage achieved) by the various embodiments of the present disclosure, for it to be encompassed by the present disclosure. In this context, the use of "may" and derivatives thereof should be understood in the sense of "may" or "optionally" rather than an affirmative capability.

Reference to the literature

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2."Prog Polym Sci 29(2004)767-814,Grafting a versatile means to modify polymers"

3.European Polym Journal,43,2007,3787-3794,Surface Modification of Polyethylene for improving the adhesion of a highly fluorinated UV-cured coating.

4. U.S. Pat. No. 5,721,315

5.International Journal of Adhesion and Adhesives 25(2005)31-38,Addition of rosin acid during thermoplastic polyurethane synthesis to improve its immediate adhesion to PVC PVC-TPU adhesion

6. U.S. Pat. No. 4,795,782

7.Polymer Vol.36pages 4587-4603,1995

8. U.S. Pat. No. 7,015,283

9.JP-03252436

10. U.S. Pat. No. 5,612,097

11.EP 1233039A1